WO2023168486A1 - Coated anode composition - Google Patents

Coated anode composition Download PDF

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Publication number
WO2023168486A1
WO2023168486A1 PCT/AU2023/050154 AU2023050154W WO2023168486A1 WO 2023168486 A1 WO2023168486 A1 WO 2023168486A1 AU 2023050154 W AU2023050154 W AU 2023050154W WO 2023168486 A1 WO2023168486 A1 WO 2023168486A1
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WIPO (PCT)
Prior art keywords
anode
active material
material particles
silicon active
anode composition
Prior art date
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PCT/AU2023/050154
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English (en)
French (fr)
Inventor
Manuel Christoph Wieser
Periyapperuma Achchige Mary Kalani ERANGI
Kai-Anders HANSEN
Khadija ALSABAWI
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Anteo Energy Technology Ltd
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Anteo Energy Technology Ltd
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Publication date
Priority claimed from AU2022900552A external-priority patent/AU2022900552A0/en
Application filed by Anteo Energy Technology Ltd filed Critical Anteo Energy Technology Ltd
Priority to CA3245526A priority Critical patent/CA3245526A1/en
Priority to CN202380026047.2A priority patent/CN118974968A/zh
Priority to JP2024553233A priority patent/JP2025508031A/ja
Priority to KR1020247033405A priority patent/KR20240167656A/ko
Priority to US18/844,569 priority patent/US20250210628A1/en
Priority to EP23765605.3A priority patent/EP4490789A1/en
Publication of WO2023168486A1 publication Critical patent/WO2023168486A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure generally relates to coated micro silicon active material particles and/or a coated anode comprising an anode composition.
  • the present disclosure also relates to an anode for a lithium-ion battery, and anode compositions thereof.
  • the present disclosure also relates to a method of incorporating the anode composition into an electrochemical cell.
  • Li-ion batteries typically employ a graphitedominant anode as an intercalation material for lithium.
  • Silicon-dominant anodes offer improvements compared to graphite-dominant Li-ion batteries.
  • Silicon (based on Li?. -Si) exhibits both higher gravimetric (3579 mAh/g vs. 372 mAh/g for graphite) and volumetric capacities (-2194 mAh/cm 3 vs. -750 mAh/cm 3 for graphite in a fully lithiated state).
  • silicon-based anodes have a low lithiation/delithiation voltage plateau at about 0.3-0.4V vs.
  • Li/Li + which allows it to maintain an open circuit potential that avoids undesirable Li plating and dendrite formation.
  • silicon shows excellent electrochemical activity, achieving a stable cycle life for silicon-based anodes is challenging due to silicon's large volume changes during lithiation and delithiation. Silicon active materials and regions may lose electrical contact from the anode as large volume changes coupled with its low electrical conductivity separate the silicon from surrounding materials in the anode.
  • SEI solid electrolyte interphase
  • an anode composition comprising micro silicon active material particles, wherein the micro silicon active material particles have one or more of the following (i) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g, (ii) a Dso particle size between about 0.1 pm and about 10 pm, and (iii) a ratio of Dso : BET surface area between about 0. 1 and about 10, wherein the amount of the micro silicon active material particles present in the anode composition is between about 60 wt.% and about 95 wt.% based on the total weight % of the anode composition, and wherein the anode composition comprises a coating.
  • the coating may be a coating of the micro silicon active material particles.
  • the coating may be selected from the group comprising carbon, graphene, graphite, metal oxide, polymer, and combinations thereof, to form a coated micro silicon active material particle.
  • the surface area of the coated micro silicon active material particle will decrease compared to the surface area of the uncoated micro silicon active material particle. It will be appreciated that in some examples, the surface area can decrease if the micro silicon active material particle had a roughened surface wherein the coating may in fact fdl these defects. In other embodiments, the surface area of the coated micro silicon active material particle will increase compared to the surface area of the uncoated micro silicon active material particle. In some embodiments, the measured BET surface area of the coated micro silicon active material particles may be between about 1 m 2 /g and about 100 m 2 /g.
  • the amount of the micro silicon active material particles or the coated micro silicon active material particles present in the anode composition may be between about 70 wt.% and about 95 wt.% based on the total weight % of the anode composition.
  • the purity of the micro silicon active material particles (without oxygen) may be at least 95 wt.%, preferably 98 wt.%.
  • the thickness of the coating may be between about 0.1 nm and about 200 nm.
  • the anode composition may further comprise one or more binders.
  • the amount of binder present in the anode composition may be between about 2.5 wt.% to about 15 wt.% based on the total weight of the anode composition.
  • the anode composition may further comprise one or more conductive materials.
  • the amount of conductive material present in the anode composition may be between about 2.5 wt.% to about 40 wt.% based on the total weight of the anode composition.
  • the micro silicon active material particles or the coated active material particles and/or the anode composition may be prelithiated.
  • the prelithiation level of the micro silicon active material particles or the coated active material particles and/or the anode composition may be between about 1% and about 30% silicon lithiation.
  • an electrochemical cell comprising: an anode; a cathode; an electrolyte; and a separator, wherein the anode comprises the anode composition defined in any one or more embodiments or examples described herein, wherein the lithium uptake capacity of the anode is greater than the lithium release capacity of the cathode.
  • the capacity of the lithium uptake capacity of the anode may not be fully utilized during charging of the lithium ion battery.
  • the anode may be only partially lithiated in the fully charged state.
  • the degree of silicon lithiation may be limited to about 20% to about 80% of the theoretical maximum.
  • a capacity ratio (N/P ratio) of the anode and the cathode may be between about 1.05 and about 7.
  • the lower cut-off voltage may be between about 2.0V and 3.5 V.
  • the pre lithiation level of the anode may be between about 1% and about 30% silicon lithiation.
  • the cathode may comprise an active material selected from the group comprising lithium nickel cobalt manganese oxide (NCM), lithium iron phosphate (LFP), lithium nickel manganese spinel (LNMO), lithium nickel cobalt aluminium oxide (NCA), lithium manganese oxide (LMO), lithium cobalt oxide (LCO), and sulphur or a sulphur composite.
  • the electrolyte may be selected from a non-aqueous electrolyte solution comprising one or more lithium salts.
  • the electrochemical cell may be an energy storage device.
  • the energy storage device may be a battery, preferably a secondary battery.
  • the battery may be a lithium-ion battery.
  • the anode within the battery delivers a specific capacity of at least about 450 mAh/g, 500 mAh/g, 600 mAh/g, 800 mAh/g, 1000 mAh/g, 1200 mAh/g, or 1500 mAh/g and retains at least about 80% of its initial capacity after 100, 200, 400, 600, 800, 1000 or 1500 cycles of the battery.
  • anode composition in an electrochemical cell, wherein the anode composition is at least partially applied to a current collector material, and wherein the anode composition is as defined by any one or more embodiments or examples described herein.
  • a process for preparing an anode for an electrochemical cell comprising the steps of: (i) preparing an anode slurry comprising micro silicon active material particles or coated micro silicon active material particles, optionally one or more further active materials, optionally one or more binders, optionally one or more conductive materials, optionally one or more additives, and a solvent system; and (ii) casting a layer of the anode slurry onto a current collector material to provide an anode composition layer on the current collector material, and (iii) optionally coating the anode composition, wherein the micro silicon active material particles have one or more of the following (a) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g, (b) a Dso particle size between about 0. 1 pm and about 10 pm, and (c) a ratio of Dso : BET surface area between about 0.1 and about 10.
  • anode prepared as defined by the process in any one or more embodiments or examples described herein.
  • process for assembling an electrochemical cell comprises the following steps: preparing an anode as defined by the process in any one or more embodiments or examples as described herein, wherein the anode comprises an anode composition as defined in any one or more embodiments or examples as described herein; and assembling the anode into an electrochemical cell.
  • Figure la is a graph showing specific coating capacity of 70wt% mSi limited capacity (with AI2O3 coating vs uncoated mSi) full cells (anode) at C/2.
  • Figure lb is a graph showing discharge capacity retention of 70wt% mSi limited capacity (with AI2O3 coating vs uncoated mSi) full cells (anode) at C/2.
  • Figure 2b is a graph showing discharge capacity retention of 70wt% mSi limited capacity (with PR coating vs uncoated mSi) full cells (anode) at C/2.
  • Figure 4a is a graph showing specific coating capacity of 70wt% mSi limited capacity (with PAN coating vs uncoated mSi) full cells (anode) at C/2.
  • Figure 4b is a graph showing discharge capacity retention of 70wt% mSi limited capacity (with PAN coating vs uncoated mSi) full cells (anode) at C/2.
  • Figure 5a is a graph showing specific coating capacity (anode) at C/2 of prelithiated 70wt% mSi anodes (at 0 and 10% prelithiation).
  • the present disclosure describes the following various non-limiting examples, which relate to investigations undertaken to identify alternative and improved anodes comprising a majority micro silicon anode composition for lithium ion batteries, to any methods of incorporating the anodes into electrochemical cells, to electrochemical cells so formed and to use thereof.
  • first Unless otherwise indicated, the terms “first,” “second,” etc. are used herein merely as labels, and are not intended to impose ordinal, positional, or hierarchical requirements on the items to which these terms refer. Moreover, reference to a “second” item does not require or preclude the existence of lower-numbered item (e.g., a “first” item) and/or a higher-numbered item (e.g., a “third” item).
  • the phrase “at least one of’, when used with a list of items, means different combinations of one or more of the listed items may be used and only one of the items in the list may be needed.
  • the item may be a particular object, thing, or category.
  • “at least one of’ means any combination of items or number of items may be used from the list, but not all of the items in the list may be required.
  • “at least one of item A, item B, and item C” may mean item A; item A and item B; item B; item A, item B, and item C; or item B and item C.
  • “at least one of item A, item B, and item C” may mean, for example and without limitation, two of item A, one of item B, and ten of item C; four of item B and seven of item C; or some other suitable combination.
  • weight % may be abbreviated to as “wt.%”.
  • lithiumation encompasses lithiation of either the anode or the cathode and is intended to denote the insertion or alloying of Li + with the active material.
  • de-lithiation encompasses lithiation of either the anode or the cathode and is intended to denote the extraction or dealloying of Li + with the active material.
  • charge can be used in the context of a full cell and a half cell.
  • the term “charge” encompasses the involuntary process of forcing Li + to migrate from the cathode into the anode upon assembly of a full cell (initial pairing of anode and cathode) and denotes a rise in the cell voltage.
  • the term “charge” encompasses the involuntary process of Li + extraction from the working electrode and deposition on the reference electrode (lithium metal foil) and denotes a rise in cell voltage.
  • discharge can be used in the context of a full cell and a half cell.
  • the term “discharge” encompasses the voluntary process of extracting Li + ions from the anode and their migration from the anode to the cathode upon assembly and denotes a decrease in the cell voltage.
  • the term “discharge” encompasses the voluntary process of Li + dissolution from the reference electrode (lithium metal foil) and the insertion of Li + into the working electrode and denotes a decrease in the cell voltage.
  • half cell describes a reference test system used for research and development purposes consisting of a working electrode (electrode of interest) and reference electrode (e.g. lithium metal foil).
  • full cell describes a conventional electrochemical cell system pairing a commercially relevant anode (graphite, silicon, LTO) with a commercially relevant cathode (LFP, LCO, NCM, NCA, LMO).
  • prelithiation describes the insertion of Li + into the anode or the anode active material before pairing with a cathode electrode in a full cell format.
  • N/P ratio or “negative to positive ratio” refers to the mass balance between the anode (negative electrode) and cathode (positive electrode). The mass balance is determined by the available area capacity per cm 2 of the respective electrodes.
  • area capacity refers to the available capacity of an electrode (anode or cathode) per area. Determined by type and wt.% of active material in the coating as well as the amount of coating loading applied to the current collector substrate in mg/cm 2 (or g/m 2 ). The higher the loading in mg/cm 2 the higher the area capacity per cm 2 .
  • the present disclosure relates, at least in part, to coated micro silicon active material particles and/or a coated anode comprising the anode composition described herein. It is believed that the coatings applied to the micro silicon active material particles, as described herein, can improve cycling stability and reduce electrolyte decomposition due to electrochemical protection of the anode surface. It will be appreciated that the coating may provide the micro silicon active particles and/or anode with one or more of a number of properties including, for example, structural strength, lower surface area, reduced pulverization, electron conductivity, Li-ion conductivity, passivation and/or insulation, and ultimately improve silicon anode capacity retention.
  • the coating may protect the surface of the micro silicon particle from ongoing contact with the electrolyte and can therefore assist in reducing or eliminating the continuous reformation of the SEI layer with every charge and discharge cycle, and the associated loss of lithium.
  • the coating should be thick enough to form an effective barrier; flexible enough to withstand the expansion behaviour of the miro silicon active material; but thin enough to avoid or minimize impeding lithium ion or electron transfer from the electrolyte to the active material and vice versa.
  • the coating is preferably electrochemically inert and so forms a passivating layer on the micro silicon particle active material surface.
  • the coating may be highly conductive.
  • a highly conductive coating may further decrease interface resistance between micro silicon particles and between those particles and the current collector.
  • the coating may tune the chemistry of an active material to provide greater affinity with binder chemistries. For example, if the binder is more hydrophobic, a more hydrophobic active material surface would have greater affinity (and vice versa).
  • the coating may reduce charge transfer resistance at the interphases and increase electronic conductivity of the micro silicon particles.
  • the coating may form a passivating layer.
  • a coating that acts as a passivating layer may prevent oxidation of the micro silicon active material once integrated into water-based anode slurries thus preventing the formation of hydrogen gas during processing while keeping the maximum amount of the micro silicon active material electrochemically active.
  • the coating may have different morphologies.
  • the resulting morphology of the coating may be subject to the coating method that is used for the purpose of applying the coating and/or the chemical nature of the precursor material or the coating material used.
  • the coating may comprise loose aggregates or particulates, including nano or micron-sized fibers, flakes, fine particles and the like, placed on or embedded into the outer surface of the micro silicon particle.
  • the particulates may have comprise a micro or nano-sized powder, fibres or flakes.
  • the coating may comprise a discontinuous layer.
  • the coating may comprise a continuous layer.
  • the coating may comprise a conformal layer.
  • the coating may present a pin-hole free of quasi pin-hole free coating.
  • the coating may be present in the anode layer from about 0. lwt.% to about 20wt.%, or from about 0. lwt.% to about 15wt.%, or from about 0. lwt.% to about 10wt.%. It will be understood that the coating wt.% will be minimized to the amount that gives the most beneficial performance to achieve the intended outcome.
  • the coating may be selected from the group comprising carbon, graphene, graphite, metal oxide, polymer, and combinations thereof, to form a coated micro silicon active material particle or a coated anode composition.
  • the thickness of the coating may be between about 0.1 nm and about 200 nm, or between about 0.2 nm and about 150 nm, or between about 0.3 nm and about 100 nm, or between about 0.3 nm and about 75 nm, or between about 0.3 nm and about 50 nm, or between about 0.3 nm and about 25 nm, or between about 0.3 nm and about 0.20 nm, or between about 0.3 nm and about 10 nm.
  • the ratio of the silicon particle diameter to coating thickness may be between about 1: 100,000 to about 1:5, or between about 1: 100,000 to about 1:8, or between about 1: 100,000 to about 1: 10, or between about 1: 100,000 to about 1: 12.
  • the silicon active material particles herein may be coated with a form of carbon.
  • the carbon coating may comprise predominantly sp 2 hybridized carbon or predominantly sp 3 hybridized carbon.
  • the carbon coating may also comprise varying degrees of sp 2 and sp 3 hybridization.
  • Some embodiments of the coating may comprise a high level of sp 2 hybridization and a low level of sp 3 hybridization or vice versa.
  • the level of sp 2 hybridization with respect to the coating may be in between 1% to 100%.
  • the level of sp3 hybridization may be in between 1% to 100%.
  • Carbon-coated silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with a carbon using one or more carbon precursors.
  • the term “carbon” may refer to an amorphous or a non-graphitizable carbon coating, a graphitic carbon coating, or graphene.
  • a non- graphitizable material is a carbon material that remains substantially amorphous even when exposed to high temperatures.
  • the carbon coatings may demonstrate a range of mixed sp 2 /sp 3 hybridization.
  • the carbon coatings may be applied using a range of techniques which are known in the art including, but not limited to, CVD, PVD, pyrolysis and the like.
  • the amorphous carbon coating may be a coating with a soft carbon or a hard carbon, as are known in the art. It will be appreciated that a wide range of precursor materials are commercially available to achieve such amorphous carbon coatings with carbon black, petroleum pitch, coal tar pitch, acetylene gas, decomposable polymers, preferably decomposable polymers with a low oxygen content, such as PVP (Polyvinylpyrrolidone), Polyacrylonitrile (PAN), polyaniline (PANi), polypyrrole (PPy), melanin resin, phenolic resin, polydopamine, resorcinol formaldehyde resin, citric acid and glucose merely being some non-limiting examples.
  • PVP Polyvinylpyrrolidone
  • PAN Polyacrylonitrile
  • PANi polyaniline
  • PPPy polypyrrole
  • melanin resin phenolic resin
  • polydopamine polydopamine
  • Amorphous carbon layers may generally be obtained via pyrolytic processes, in which the micro silicon particle would be exposed to a decomposable gas such as acetylene which then deposits on the surface as a layer of carbon when heated to a sufficiently high temperature.
  • they may be obtained by coating the micro silicon particles in a pre-cursor material such as pitch or combustible polymers and pyrolyzing the pitch or polymer to form a carbon layer.
  • a pre-cursor material such as pitch or combustible polymers
  • Different carbon precursors can be selected to form different qualities of carbon layer. For example, aromatic compounds may form a quality coating which may have a higher degree of sp 2 hybridization. More linear organic compounds such as acetylene or certain polymers may form more amorphous structures with a higher degree of sp 3 hybridization.
  • graphene -coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with graphene.
  • the graphene may be selected from the group comprising graphene, graphene oxide or reduced graphene oxide and derivatives thereof.
  • Graphite -coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with graphite.
  • the graphite may be selected from the group comprising graphite, nano graphite, graphite oxide and derivatives thereof.
  • Metal oxide-coated micro silicon particles may be provided by coating the micro silicon active material particles, as described herein, with a metal oxide.
  • the metal oxide may be selected from the group comprising aluminium oxide, aluminium oxide hydroxide (y-AlO(OH)), aluminium hydroxide (Al(0H)3), aluminium nitrate (A1(NO3)3) or other comparable aluminium containing species.
  • the aluminium hydroxide or the aluminium nitrate may form a precursor for subsequent conversation to aluminium oxide hydroxide or aluminium oxide.
  • the aluminium oxide may comprise alpha aluminium oxide.
  • the metal oxide may comprise titanium or niobium based metal oxide.
  • the metal oxide coating may comprise titanium oxide (TiCh) or niobium oxide (Nb2C>5).
  • the metal oxide coating may comprise a magnesium based oxide.
  • the magnesium based oxide may be magnesium oxide (MgO).
  • metal oxides such as for example a-aluminium oxide and other aluminium species, may be applied to the micro silicon particles via either precipitation processes followed by calcination at higher temperatures of >400 °C or via processes such as atomic layer deposition (ALD).
  • the precipitation process route typically involves dissolving the appropriate metal salt in water at an appropriate concentration and under controlled pH and manipulating the pH so that the metal salt uniformly precipitates on the surface of the micro silicon active material. Typically this involves raising the pH of the environment. The concentration of the metal salt in solution determines the final coating layer thickness. Excess components and metal salt may be gently washed and the micro silicon active material may be transferred into a furnace. The precipitate may be heated under air or an inert gas to a temperature of up 1200°C which converts the metal salt precursor to the corresponding metal oxide.
  • Polymer-coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with a polymer.
  • the polymer may be selected from the group comprising starch, lignin, cellulose, polyacrylamide, polymethacrylamide, polyamic acid, polystyrene-4- sulfonate (PSS), 3,4-ethylenedioxythiophene/polystyrene-4-sulfonate (PEDOT:PSS), polydiallyldimethylammonium chloride PDDA, polydiallyldimethylammonium/polystyrene-4-sulfonate (PDDA:PSS), urea- pyrimidinone (UPy), urea-oligo-amidoamine (UOAA), dopamine methacrylamide, dopamine methacrylate, dopamine acrylate, dopamine, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxy
  • the coated micro silicon active material particles may be provided from precipitation, pyrolization of a precursor formulation coating or by chemical vapour deposition, physical vapour deposition, atomic layer deposition sputtering, or mechanical deposition.
  • the coating may be in the form of a single layer on the surface of the micro silicon active material particle.
  • the coating may be in the form of two or more layers, for example, a plurality of layers on the surface of the micro silicon active material particle.
  • the coating may comprise between about 1 to 5 layers.
  • the coating may comprise less than 5 layers, 4 layers, 3 layers, or less than 2 layers.
  • the coating may comprise at least about 1 layer, 2 layers, 3 layers, 4 layers, or at least about 5 layers.
  • the coating may comprise layers in a range provided by any lower and/or upper limit as previously described. It will be appreciated that each layer may be provided by a different coating.
  • the coated micro silicon active material particles may comprise a coating, wherein a coating layer comprises a graphene and a further coating layer comprises a metal oxide (e.g., aluminium oxide), applied in either order to the micro silicon.
  • a metal oxide e.g., aluminium oxide
  • coated micro silicon active material particles may present any morphology, for example they may take the form of flakes, agglomerates, granules, powders, spheres, pulverized materials or the like, as well as combinations thereof.
  • the coated micro silicon active material particles may have any desired shape including, but not limited to, cubic, rod like, plate-like, polyhedral, spherical or semi-spherical, quasi spherical, rounded or semi-rounded, angular, irregular, and so forth.
  • the coated micro silicon active material particles have an aspect ratio (i.e.
  • the particle size (in pm) of the coated micro silicon active material particles may be at least about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, or 50. In some embodiments, the particle size (in pm) of the coated micro silicon active material particles may be less than about 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.5. Combinations of any two or more of these upper and/or lower particle sizes are also possible, for example the particle size (in pm) of the coated micro silicon active material particles may be between about 1 to about 50, about 2 to about 40, or about 3 to about 30. The particle size is taken to be the longest cross-sectional diameter across a coated micro silicon active material particle. For non- spherical coated micro silicon active material particles, the particle size is taken to be the distance corresponding to the longest cross-section dimension across the particle.
  • the coated micro silicon active material particles may have a particle size distribution, wherein 90% of the micro silicon active material particles (D90) have a particle size of less than about 50, 45, 40, 35, 34, 32, 30, 28, 24, 20, 18, 16, 14, 12, 10, 8, 6, 5 or 4 pm, wherein 50 % of the micro silicon active material particles (D50) have a particle size (in pm) of less than about 10, 9, 8 7, 6, 5, 4, 3, 2, 1, 0.8, 0.6, 0.4, 0.2, 0.1, or wherein 10 % of the micro silicon active material particles (Dio) have a particle size of less than about 4, 3, 2, or 1 pm.
  • the micro silicon active material particles have a (Dso) particle size (in pm) of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In some embodiments, the micro silicon active material particles have a (Dso) particle size (in pm) of less than about 10, 9, 8, 7, 6, 5, 4, 3.5, 3, 2.5, 2, 1. 0.9, 0.8, 0.7, 0.6, 0.5, 0.5, 0.4, 0.3, 0.2, or 0.1.
  • the micro silicon active material particles have a (Dso) particle size (in pm) of between about 0.1 to about 10, about 0.1 to about 9, about 0.1 to about 8, about 0.1 to about 7, about 0. 1 to about 6, about 0. 1 to about 5, about 0.5 to about 10, about 0.5 to about 9, about 0.5 to about 8, about 0.5 to about 7, about 0.5 to about 6, about 0.5 to about 5, about 1 to about 10, about 1 to about 9, about 1 to about 8, about 1 to about 7, about 1 to about 6, or about 1 to about 5.
  • a (Dso) particle size (in pm) of between about 0.1 to about 10, about 0.1 to about 9, about 0.1 to about 8, about 0.1 to about 7, about 0. 1 to about 6, about 0. 1 to about 5, about 0.5 to about 10, about 0.5 to about 9, about 0.5 to about 8, about 0.5 to about 7, about 0.5 to about 6, or about 1 to about 5.
  • the coated micro silicon active material particles may have a BET surface area in a range of from about 0.1 m 2 /g to about 100 m 2 /g.
  • the coated micro silicon active material particles may have a BET surface area (m 2 /g) of at least about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 m 2 /g.
  • the coated micro silicon active material particles may have a surface area (m 2 /g) of less than about 100, 90, 80, 70, 60, 50, 45, 40, 35, 30, 25, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2 1, 0.5, or 0.1 m 2 /g. Combinations of these surface area values to form various ranges are also possible.
  • the tap density of the coated micro silicon active material particles may be in a range of from about 0.5 g/cm 3 to about 1.5 g/cm 3 .
  • the tap density of the coated micro silicon active material particles may be at least about 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.2, 1.3 or 1.5 g/cm 3 .
  • the tap density of the coated micro silicon active material particles may be less than about 1.5, 1.4, 1.3, 1.2, 1.0, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, or 0.5 g/cm 3 .
  • the coated micro silicon active material particles may have a tap density of between about 0.5 g/cm 3 to about 1.2 g/cm 3 .
  • the density can be measured by any standard method, for example in accordance with ASTM D7481-18.
  • the purity of micro silicon active material particles (with oxygen) may be in a range from (by wt.%) about 79 to about 99.5.
  • the purity of micro silicon active material particles (with oxygen) may be at least (by wt.%) about 75, 80, 85, 90, 95, 96, 97, 98, 99 or 99.5.
  • the purity of the micro silicon active material particles (with oxygen) may be less than (by wt.%) about 99.5, 99, 98, 97, 96, 95, 90, 85, 80, or 75.
  • the purity of micro silicon active material particles (with oxygen) may be in a range provided by any lower and/or upper limit as previously described.
  • the combination of novel and inventive features of the coated micro silicon active material particles according to the present disclosure and its use in an anode composition for an anode in a lithium ion battery may also surprisingly lead to an improvement in the batteries cycle behaviour. It was unexpectedly shown that the lithium-ion batteries, as described herein, have a small irreversible capacity loss in the first charge cycle and a stable electrochemical behaviour with minimal fading in the subsequent cycles. Therefore, with the use of the coated micro silicon active material particles, as described herein, a lower initial capacity loss and also a low continuous loss of capacity of the lithium-ion batteries can be achieved. Overall, the lithium-ion batteries as described herein provide very good stability and cycle life. Accordingly, a high number of cycles can be achieved with minimal fatigue, for example, as a consequence of mechanical destruction of the anode coating layer, anode material or SEI formation.
  • the present disclosure is directed to providing improvements in anodes for lithium ion batteries.
  • the present disclosure covers various research and development directed to identifying and better understanding the failure mechanisms of anodes comprising majority silicon anode compositions and subsequently optimising their formulations such that the degradation (e.g., cracking and delamination), silicon particle fracturing and instability of the solid electrolyte interphase can be controlled, reduced or in some manner ameliorated to improve stability and cyclability of the lithium ion battery.
  • the majority silicon anode composition can demonstrate significant stability and/or cycle life of an anode. It has further been surprisingly found that the majority silicon anode composition paired with the method of integration into the electrochemical cell can control the formation of SEI and the expansion and degradation of silicon, and therefore significantly extend the stability and/or cycle life of the anode.
  • the majority silicon anode composition for an electrochemical cell e.g. battery
  • the majority silicon anode composition for an electrochemical cell may provide one or more further advantages such as:
  • the anode composition as described herein may comprise micro silicon active material particles, wherein the micro silicon active material particles have one or more of the following (i) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g, (ii) a Dso particle size between about 0.1 pm and about 10 pm, and (iii) a ratio of Dso : BET surface area between about 0.1 and 10, and wherein the amount of silicon present in the anode composition is between about 60 wt.% and about 95 wt.% based on the total weight % of the anode composition.
  • the anode composition as described herein may comprise micro silicon active material particles, wherein the micro silicon active material particles have (i) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g and (ii) a Dso particle size between about 0. 1 pm and about 10 pm, or (iii) a ratio of Dso : BET surface area between about 0.1 and 10, and wherein the amount of silicon present in the anode composition is between about 60 wt.% and about 95 wt.% based on the total weight % of the anode composition.
  • the anode composition as described herein may comprise or consist of the micro silicon active material particles, as described herein, optionally one or more further active materials, optionally one or more binders, optionally one or more conductive materials, and optionally one or more additives.
  • the anode composition as described herein may comprise or consist of micro silicon active material particles, wherein the micro silicon active material particles have one or more of the following (i) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g, (ii) a Dso particle size between about 0.1 pm and about 10 pm, and (iii) a ratio of Dso : BET surface area between about 0.1 and 10, wherein the micro silicon active material particles are coated, and wherein the amount of the coated micro silicon active material particles present in the anode composition is between about 60 wt.% and about 95 wt.% based on the total weight % of the anode composition; optionally one or more further active materials, optionally one or more binders; optionally one or more conductive materials; and optionally one or more additives.
  • the anode composition as described herein may comprise micro silicon active material particles, wherein the micro silicon active material particles have (i) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g and (ii) a D50 particle size between about 0. 1 pm and about 10 pm, or (iii) a ratio of Dso : BET surface area between about 0.
  • micro silicon active material particles are coated, and wherein the amount of the coated micro silicon active material particles present in the anode composition is between about 60 wt.% and about 95 wt.% based on the total weight % of the anode composition; optionally one or more further active materials, optionally one or more binders; optionally one or more conductive materials; and optionally one or more additives.
  • the micro silicon active material particles content of the anode composition may be between about 60 wt.% and about 95 wt.% based on the total weight of the anode composition. It will be appreciated that further advantages may be shown when the micro silicon active material particles content of the anode composition is greater than 60 wt.%, preferably greater than 70 wt.%.
  • the micro silicon active material particles content may be less than about 95 wt.%, 90 wt.%, 85 wt.%, 80 wt.%, 75 wt.%, 70 wt.%, 65 wt.%, or 60 wt.%.
  • the micro silicon active material particles content may be at least about 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, or 95 wt.%.
  • the micro silicon active material particles content of the anode composition may be in a range provided by any two of these upper and/or lower amounts.
  • the anode composition may be supported on a current collector material.
  • the anode composition may be applied to the current collector material as a coating or fdm. It will be understood that the current collector may be at least partially coated with the anode composition.
  • the anode composition may be applied to only one side of the current collector material.
  • the current collector material for the anode may be selected from the group comprising copper, aluminium, stainless steel, titanium, carbon, perforated metal foils, metal foams, and metal coated polymer based porous and non-porous membranes. It will be appreciated that the current collector material will be of appropriate dimension, porosity and pore size, encompassing the above materials and acting as the current collector.
  • the anode composition may be applied to a copper current collector material (e.g. copper foil).
  • a copper current collector material e.g. copper foil
  • the anode composition comprising or consisting of micro silicon active material particles, optionally one or more further active materials, optionally one or more binders, optionally one or more conductive materials, and optionally one or more additives, may be supported on a copper current collector material (e.g. copper foil).
  • the current collector material for the anode may have a thickness of between about 4 pm and about 25 pm.
  • the thickness of the current collector (in pm) may be less than about 25, 20, 15, 10, 8, 6, or 4.
  • the thickness of the current collector (in pm) may be at least about 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, or 25.
  • the thickness of the current collector (in pm) may be in a range provided by any two of these upper and/or lower amounts.
  • the current collector material for the anode may be copper foil having a thickness of between about 6 pm and about 12 pm.
  • the anode composition may be an anode for a battery.
  • the anode composition may be an anode for a lithium ion battery.
  • the present disclosure may also be directed to an anode composition comprising a coating.
  • the coating may be a coating of the micro silicon active material particles which are subsequently incorporated into the anode composition.
  • the coating may be a coating of the anode composition or anode itself.
  • the coating may be present on at least a portion of the surface of the anode composition and the anode so formed.
  • the portion (%) may be at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100.
  • the coating may be selected from the group comprising carbon, graphene, graphite, metal oxide, polymer, and combinations thereof, to form a coated micro silicon active material particle or a coated anode composition.
  • the silicon active material particles herein may be coated with a form of carbon.
  • the carbon coating may comprise predominantly sp 2 hybridized carbon or predominantly sp 3 hybridized carbon.
  • the carbon coating may also comprise varying degrees of sp 2 and sp 3 hybridization.
  • Some embodiments of the coating may comprise a high level of sp 2 hybridization and a low level of sp 3 hybridization or vice versa.
  • the level of sp 2 hybridization with respect to the coating may be in between 1% to 100%.
  • the level of sp3 hybridization may be in between 1% to 100%.
  • a particular coating embodiment may comprise a level of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80, 90%, 99% or 100% sp 2 hybridization which may be combined with a level of sp 3 hybridization of 1 - % sp 2 hybridization * 100.
  • the remainder of the coating is made up of the sp 3 hybridization.
  • Another coating embodiment may comprise a level of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80, 90% or 100% sp 3 hybridization whereas the level of sp 2 hybridization is 1 - % sp 3 hybridization * 100.
  • the amorphous carbon coating may be a coating with a soft carbon or a hard carbon, as are known in the art. It will be appreciated that a wide range of precursor materials are commercially available to achieve such amorphous carbon coatings with carbon black, petroleum pitch, coal tar pitch, acetylene gas, decomposable polymers, preferably decomposable polymers with a low oxygen content, such as PVP (Polyvinylpyrrolidone), Polyacrylonitrile (PAN), polyaniline (PANi), polypyrrole (PPy), melanin resin, phenolic resin, polydopamine, resorcinol formaldehyde resin, citric acid and glucose merely being some non-limiting examples.
  • PVP Polyvinylpyrrolidone
  • PAN Polyacrylonitrile
  • PANi polyaniline
  • PPPy polypyrrole
  • melanin resin phenolic resin
  • polydopamine polydopamine
  • Amorphous carbon layers may generally be obtained via pyrolytic processes, in which the micro silicon particle would be exposed to a decomposable gas such as acetylene which then deposits on the surface as a layer when heated to a sufficiently high temperature.
  • they may be obtained by coating the micro silicon particles in a pre-cursor material such as pitch or combustible polymers and pyrolyzing the pitch or polymer to form a carbon layer.
  • a pre-cursor material such as pitch or combustible polymers
  • Different carbon precursors can be selected to form different qualities of carbon layer. For example, aromatic compounds may form a quality coating which may have a higher degree of sp 2 hybridization. More linear organic compounds such as acetylene or certain polymers may form more amorphous structures with a higher degree of sp 3 hybridization.
  • graphene -coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with graphene.
  • the graphene may be selected from the group comprising graphene, graphene oxide or reduced graphene oxide and derivatives thereof.
  • Graphite -coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with graphite.
  • the graphite may be selected from the group comprising graphite, nano graphite, graphite oxide and derivatives thereof.
  • Metal oxide-coated micro silicon particles may be provided by coating the micro silicon active material particles, as described herein, with a metal oxide.
  • the metal oxide may be selected from the group comprising aluminium oxide, aluminium oxide hydroxide (y-AlO(OH)), aluminium hydroxide (Al(0H)3), aluminium nitrate (A1(NO3)3) or other comparable aluminium containing species.
  • the aluminium hydroxide or the aluminium nitrate may form a precursor for subsequent conversation to aluminium oxide hydroxide or aluminium oxide.
  • the aluminium oxide may comprise alpha aluminium oxide.
  • the metal oxide may comprise titanium or niobium based metal oxide.
  • the metal oxide coating may comprise titanium oxide (TiCh) or niobium oxide (NbrOs).
  • the metal oxide coating may comprise a magnesium based oxide.
  • the magnesium based oxide may be magnesium oxide (MgO).
  • metal oxides such as for example a-aluminium oxide and other aluminium species, may be applied to the micro silicon particles via either precipitation processes followed by calcination at higher temperatures of >400 °C or via processes such as atomic layer deposition (ALD).
  • the precipitation process route typically involves dissolving the appropriate metal salt in water at an appropriate concentration and under controlled pH and manipulating the pH so that the metal salt uniformly precipitates on the surface of the micro silicon active material. Typically this involves raising the pH of the environment. The concentration of the metal salt in solution determines the final coating layer thickness. Excess components and metal salt may be gently washed and the micro silicon active material may be transferred into a furnace. The precipitate may be heated under air or an inert gas to a temperature of up 1200°C which converts the metal salt precursor to the corresponding metal oxide.
  • Polymer-coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with a polymer.
  • the polymer may be selected from the group comprising starch, lignin, cellulose, polyacrylamide, polymethacrylamide, polyamic acid, polystyrene-4- sulfonate (PSS), 3,4-ethylenedioxythiophene/polystyrene-4-sulfonate (PEDOT:PSS), polydiallyldimethylammonium chloride PDDA, polydiallyldimethylammonium/polystyrene-4-sulfonate (PDDA:PSS), urea- pyrimidinone (UPy), urea-oligo-amidoamine (UOAA), dopamine methacrylamide, dopamine methacrylate, dopamine acrylate, dopamine, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxy
  • Silane coupling agent derived coatings on micro silicon active material particles may be provided by a silane coupling agent represented by the following formula (1): Y-(CH2)n-Si-X3 wherein Y represents a non-hydrolytic group that is capable of forming a conductive polymer moiety, a conductive coating layer, a lithium- ion conducting coating layer, a layer that advantageously interacts with the electrode binder via physical attractive forces or binding, a layer that advantageously interacts with the electrode binder via forming chemical bonds, or a combination of any of the above upon polymerization on the active material surface; each X independently represents a hydroxyl group, or a hydrolysable group selected from the group consisting of halogen atoms, alkoxy groups, ether groups and siloxy groups; the three X groups may be identical with or different from each other; and n represents an integer from 0 to 3.
  • Y represents a non-hydrolytic group that is capable of forming a conductive polymer moiety, a
  • Y may comprise amino, epoxy, polyethylene glycol methyl ether, polyethylene gylcol, acryloxy, methacryloxy functionalities or any combination thereof.
  • Examples of the silane coupling agents represented by formula (1) may include but are not limited to, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis-gamma trimethoxysilypropylamine, aminoneohexyltrimethoxy silane .
  • the coated micro silicon active material particles or coated anode composition may be provided in any manner or embodiment as described above, including pyrolization of a coating or by chemical vapour deposition, physical vapour deposition, sputtering, or mechanical deposition.
  • the coating may be in the form of a single layer.
  • the coating may be in the form of two or more layers, for example, a plurality of layers.
  • the coating may comprise between about 1 to 5 layers.
  • the coating may comprise less than 5 layers, 4 layers, 3 layers, or less than 2 layers.
  • the coating may comprise at least about 1 layer, 2 layers, 3 layers, 4 layers, or at least about 5 layers.
  • the coating may comprise layers in a range provided by any lower and/or upper limit as previously described. It will be appreciated that each layer may be provided by a different coating.
  • the coated micro silicon active material particles or coated anode composition may comprise a coating, wherein one coating layer comprises a carbon material another coating layer comprises a metal oxide (e.g., aluminium oxide) and another layer comprises a polymeric coating, applied in any order to the micro silicon.
  • the coating may be a carbon material coating and a metal oxide coating, applied in either order to the micro silicon.
  • the coating may be a carbon material coating and a polymeric coating, applied in either order to the micro silicon.
  • the coatings on the micro silicon active material particles or the anode composition can improve cycling stability and reduce electrolyte decomposition due to electrochemical protection of the anode surface. It will be appreciated that the coating may provide the micro silicon active particles or anode composition with a number of properties including, for example, structural strength, lower surface area, reduced pulverization, electron conductivity, Li-ion conductivity, passivation and/or insulation, and ultimately improve silicon anode capacity retention.
  • the present invention relates to an anode composition comprising optionally coated micro silicon active material particles.
  • the present invention also relates to an anode composition comprising coated micro silicon active material particles.
  • the micro silicon active material particles may be selected from the group comprising or consisting of metallurgical silicon, polycrystalline silicon and monocrystalline silicon.
  • the micro silicon active material particles are metallurgical silicon.
  • the raw feedstock for any type of elemental silicon is quartz sand (silicon dioxide (SiCh)).
  • SiOr is reacted with carbon in arc furnaces, where the carbon may be supplied to the process in the form of coke and where were high temperatures ( ⁇ 1800°C), are applied to reduce the SiOr to Si and CO according to the following reaction:
  • Metallurgical grade silicon which may comprise impurities such as Al, Ca, Fe, Ti, P, Cu, Cr, K, V, Ni, Na and others at levels of several hundred to several thousand parts per million (ppm).
  • Metallurgical silicon can be used in various industrial applications including steel production. However, due to the impurities, it cannot be used for electronic applications.
  • the crystal structure of metallurgical silicon is well-defined, but it is neither as pure nor efficient at conducting electricity as monocrystalline silicon.
  • Metallurgical silicon has a metallic crystal structure, which is characterized by its metallic bonding between atoms. In the metallic crystal structure, atoms are arranged in a repeating pattern, but lacking order.
  • chloride impurities may also form such as FeCh, but due to the differences between the boiling point of these impurities and SiHCh, the fractional distillation technique can be used to separate the impurities.
  • the mixture of SiHCh and the chloride impurities are heated, where the vapours are condensed in different distillation towers and held at appropriate temperatures. This will enable the separation of pure SiHCh from the impurities.
  • a reaction between SiHCh and H2 will result in forming pure polycrystalline silicon. 2SiHCl 3 + 2H 2 ⁇ 2Si + 6HCI .
  • the crystal structure of poly crystalline silicon is not well-defined, and the small crystals (grain) that make up the material are randomly oriented and typically less than 100 micrometers in size. The grains are separated by grain boundaries and normally have random crystallographic orientations. This results in material that is weaker than monocrystalline silicon and is less efficient at conducting electricity.
  • Czochralski method is used to convert the pure poly crystalline silicon to single-crystal monocrystalline silicon.
  • a seed crystal is required to grow single- crystal material, which will act as a template for growth.
  • Czochralski method involves heating the polycrystalline silicon in a quartz-lined graphite crucible by resistively heating it to the melting point of Si (1412°C). Then a seed crystal is lowered into the molten material and raised slowly allowing the crystal to grow onto the seed. During the growth of the crystal a slow rotation is required to average out any temperature variations that might result in an inhomogeneous solidification.
  • the resulting monocrystalline silicon is often referred to as single-crystal silicon. It consists of silicon, which is characterized by its regular and repeating arrangement of atoms in a three-dimensional lattice, and free from grain limits. Monocrystalline silicon can be treated as an intrinsic semiconductor consisting only of excessively pure silicon. Monocrystalline silicon is known for its high efficiency and high purity, making it ideal for use in electronic applications. Mono-crystalline silicon can be a p-type and n-type silicon by doping with other elements.
  • impurities may be present in any micro silicon active material particle. It is also well known that impurities may be selectively added to any micro silicon active material particle. In some embodiments, impurities selected from the group consisting of Al, Ca, Fe, Ti, P, Cu, Cr, K, V, Ni and Na may be present in the micro silicon active material particle, for example in a total or individual amount of less than about 5000 ppm, less than about 4500 ppm, less than about 4000 ppm, less than about 3500 ppm, or less than about 3000 ppm.
  • total or individual impurities selected from the group consisting of Al, Ca, Fe, Ti, P, Cu, Cr, K, V, Ni and Na may be present in the micro silicon active material particle in a range between about 0 ppm and about 5000 ppm, preferably between about 0 ppm and about 4000 ppm, more preferably between about 0 ppm and about 3000 ppm.
  • the micro silicon active material particles are coated micro silicon active material particles, as described herein, and the anode composition comprising the coated micro silicon active material particles may or may not be additionally coated.
  • the micro silicon active material particle coating may be selected from the group comprising carbon, graphene, graphite, metal oxide, polymer, and combinations thereof, to form a coated micro silicon active material particle or a coated anode composition.
  • the thickness of the coating may be between about 0.1 nm and about 200 nm, or between about 0.2 nm and about 150 nm, or between about 0.3 nm and about 100 nm, or between about 0.3 nm and about 75 nm, or between about 0.3 nm and about 50 nm, or between about 0.3 nm and about 25 nm, or between about 0.3 nm and about 20 nm, or between about 0.3 nm and about 10 nm.
  • the thickness of the coating may be less than about 200, 175, 150, 125, 100, 90, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 8, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1.
  • the ratio of the silicon particle diameter to coating thickness may be between about 1: 100,000 to about 1:5, or between about 1: 100,000 to about 1:8, or between about 1: 100,000 to about 1: 10, or between about 1: 100,000 to about 1: 12.
  • a particular coating embodiment may comprise a level of 10%, 20%, 30%, 50%, 60%, 70%, 80, 90%, 99% or 100% sp 2 hybridization which may be combined with a level of sp 3 hybridization of 1 - % sp 2 hybridization * 100.
  • the remainder of the coating is made up of the sp 3 hybridization.
  • Another coating embodiment may comprise a level of 10%, 20%, 30%, 50%, 60%, 70%, 80, 90% or 100% sp 3 hybridization whereas the level of sp 2 hybridization is 1 - % sp 3 hybridization * 100.
  • Carbon-coated silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with a carbon using one or more carbon precursors.
  • the term “carbon” may refer to an amorphous or a non-graphitizable carbon coating, a graphitic carbon coating, or graphene.
  • a non- graphitizable material is a carbon material that remains substantially amorphous even when exposed to high temperatures.
  • the carbon coatings may demonstrate a range of mixed sp 2 /sp 3 hybridization.
  • the carbon coatings may be applied using a range of techniques which are known in the art including, but not limited to, CVD, PVD, pyrolysis and the like.
  • the amorphous carbon coating may be a coating with a soft carbon or a hard carbon, as are known in the art. It will be appreciated that a wide range of precursor materials are commercially available to achieve such amorphous carbon coatings with carbon black, petroleum pitch, coal tar pitch, acetylene gas, decomposable polymers, preferably decomposable polymers with a low oxygen content, such as PVP (Polyvinylpyrrolidone), Polyacrylonitrile (PAN), polyaniline (PANi), polypyrrole (PPy), melanin resin, phenolic resin, polydopamine, resorcinol formaldehyde resin, citric acid and glucose merely being some non-limiting examples.
  • PVP Polyvinylpyrrolidone
  • PAN Polyacrylonitrile
  • PANi polyaniline
  • PPPy polypyrrole
  • melanin resin phenolic resin
  • polydopamine polydopamine
  • Amorphous carbon layers may generally be obtained via pyrolytic processes, in which the micro silicon particle would be exposed to a decomposable gas such as acetylene which then deposits on the surface as a layer when heated to a sufficiently high temperature.
  • they may be obtained by coating the micro silicon particles in a pre-cursor material such as pitch or combustible polymers and pyrolyzing the pitch or polymer to form a carbon layer.
  • a pre-cursor material such as pitch or combustible polymers
  • Different carbon precursors can be selected to form different qualities of carbon layer. For example, aromatic compounds may form a quality coating which may have a higher degree of sp 2 hybridization. More linear organic compounds such as acetylene or certain polymers may form more amorphous structures with a higher degree of sp 3 hybridization.
  • graphene -coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with graphene.
  • the graphene may be selected from the group comprising graphene, graphene oxide or reduced graphene oxide and derivatives thereof.
  • Graphite -coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with graphite.
  • the graphite may be selected from the group comprising graphite, nano graphite, graphite oxide and derivatives thereof.
  • metal oxides such as for example a-aluminium oxide and other aluminium species, may be applied to the micro silicon particles via either precipitation processes followed by calcination at higher temperatures of >400 °C or via processes such as atomic layer deposition (ALD).
  • the precipitation process route typically involves dissolving the appropriate metal salt in water at an appropriate concentration and under controlled pH and manipulating the pH so that the metal salt uniformly precipitates on the surface of the micro silicon active material. Typically this involves raising the pH of the environment. The concentration of the metal salt in solution determines the final coating layer thickness. Excess components and metal salt may be gently washed and the micro silicon active material may be transferred into a furnace. The precipitate may be heated under air or an inert gas to a temperature of up 1200°C which converts the metal salt precursor to the corresponding metal oxide.
  • Polymer-coated micro silicon active material particles may be provided by coating the micro silicon active material particles, as described herein, with a polymer.
  • the polymer may be selected from the group comprising starch, lignin, cellulose, polyacrylamide, polymethacrylamide, polyamic acid, polystyrene-4- sulfonate (PSS), 3,4-ethylenedioxythiophene/polystyrene-4-sulfonate (PEDOT:PSS), polydiallyldimethylammonium chloride PDDA, polydiallyldimethylammonium/polystyrene-4-sulfonate (PDDA:PSS), urea- pyrimidinone (UPy), urea-oligo-amidoamine (UOAA), dopamine methacrylamide, dopamine methacrylate, dopamine acrylate, dopamine, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxy
  • PVdF poly(bis-(methoxyethoxy)ethoxy)phosphazene
  • PVDF-HFP poly(vinylidene fluoride)-hexafluoropropylene
  • any derivatives thereof e.g. sulfonated derivatives
  • phenolic resin or any combination thereof.
  • the coated micro silicon active material particles may be provided from precipitation, pyrolization of a precursor formulation coating or by chemical vapour deposition, physical vapour deposition, atomic layer deposition sputtering, or mechanical deposition.
  • the coating may be in the form of a single layer. In another embodiment, the coating may be in the form of two or more layers, for example, a plurality of layers.
  • the coating may comprise between about 1 to 5 layers.
  • the coating may comprise less than 5 layers, 4 layers, 3 layers, or less than 2 layers.
  • the coating may comprise at least about 1 layer, 2 layers, 3 layers, 4 layers, or at least about 5 layers.
  • the coating may comprise layers in a range provided by any lower and/or upper limit as previously described. It will be appreciated that each layer may be provided by a different coating.
  • the coated micro silicon active material particles or coated anode composition may comprise a coating, wherein one coating layer comprises a carbon material another coating layer comprises a metal oxide (e.g., aluminium oxide) and another layer comprises a polymeric coating, applied in any order to the micro silicon.
  • the coating may be a carbon material coating and a metal oxide coating, applied in either order to the micro silicon.
  • the coating may be a carbon material coating and a polymeric coating, applied in either order to the micro silicon.
  • the coatings on the micro silicon active material particles can improve cycling stability and reduce electrolyte decomposition due to electrochemical protection of the anode surface. It will be appreciated that the coating may provide the micro silicon active particles with a number of properties including, for example, structural strength, lower surface area, reduced pulverization, electron conductivity, Li-ion conductivity, and/or insulation, and ultimately improve silicon anode capacity retention.
  • the micro silicon active material particles or coated micro silicon active material particles may present any morphology, for example they may take the form of flakes, agglomerates, granules, powders, spheres, pulverized materials or the like, as well as combinations thereof.
  • micro silicon active material particles or coated micro silicon active material particles may have any desired shape including, but not limited to, cubic, rod like, plate-like, polyhedral, spherical or semi-spherical, quasi spherical, rounded or semi-rounded, angular, irregular, and so forth.
  • the micro silicon active material particles or coated micro silicon active material particles have an aspect ratio (i.e. the ratio of a length to a width, where the length and width are measured perpendicular to one another, and the length refers to the longest linearly measured dimension) of 1.0 to 10.0, 1.0 to 5.0, or 1.0 to 2.0.
  • the micro silicon active material particles or coated micro silicon active material particles may have an aspect ratio of about 1.0 to 5.0 or about 1.0 to 4.0 or about 1.0 to about 3.0, or about 1.0 to about 2.0, for example about 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5.0.
  • the particle size (in pm) of the micro silicon active material particles or coated micro silicon active material particles may be at least about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, or 30. In some embodiments, the particle size (in pm) of the micro silicon active material particles or coated micro silicon active material particles may be less than about 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.5. Combinations of any two or more of these upper and/or lower particle sizes are also possible, for example the particle size (in pm) of the micro silicon active material particles or coated micro silicon active material particles may be between about 1 to about 10, about 2 to about 8, about 3 to about 6, or about 2 to about 5.
  • the micro silicon active material particles may have a particle size distribution, wherein 90 % of the micro silicon active material particles (D90) have a particle size of less than about 50, 45, 40, 35, 34, 32, 30, 28, 24, 20, 18, 16, 14, 12, 10, 8, 6, 5 or 4 pm, wherein 50 % of the micro silicon active material particles (Dso) have a particle size (in pm) of less than about 10, 9, 8, 7, 6, 5, 4, 3, 2 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1, or wherein 10 % of the micro silicon active material particles (Dio) have a particle size of less than about 4, 3, 2, or 1.
  • the micro silicon active material particles have a (Dso) particle size (in pm) of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In some embodiments, the micro silicon active material particles have a (Dso) particle size (in pm) of less than about 10, 9, 8, 7, 6, 5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9. 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1.
  • the micro silicon active material particles have a (Dso) particle size (in pm) of between about 0.1 to about 10, about 0.1 to about 9, about 0.1 to about 8, about 0.1 to about 7, about 0. 1 to about 6, about 0. 1 to about 5, about 0.5 to about 10, about 0.5 to about 9, about 0.5 to about 8, about 0.5 to about 7, about 0.5 to about 6, about 0.5 to about 5, about 1 to about 10, about 1 to about 9, about 1 to about 8, about 1 to about 7, about 1 to about 6, or about 1 to about 5.
  • a (Dso) particle size (in pm) of between about 0.1 to about 10, about 0.1 to about 9, about 0.1 to about 8, about 0.1 to about 7, about 0. 1 to about 6, about 0. 1 to about 5, about 0.5 to about 10, about 0.5 to about 9, about 0.5 to about 8, about 0.5 to about 7, about 0.5 to about 6, or about 1 to about 5.
  • the micro silicon active material particles may have a BET surface area in a range of from about 0. 1 m 2 /g to about 10 m 2 /g, for example from about 0.1 m 2 /g to about 5 m 2 /g.
  • the micro silicon active material particles may have a BET surface area (m 2 /g) of at least about 0.1, 0.2 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 m 2 /g.
  • the coated micro silicon active material particles may have a BET surface area in a range of from about 0.1 m 2 /g to about 90 m 2 /g.
  • the inventors have surprisingly found that there is a relationship between the Dso particle size (in pm) of the uncoated micro silicon active material particles and the BET surface area (m 2 /g) of the uncoated micro silicon active material particles, and the ratio of those parameters to the electrochemical performance of the anode.
  • the ratio of D50 particle size (in pm) of the micro silicon active material particles and the BET surface area (m 2 /g) of the micro silicon active material particles may be in a range from about 0. 1 to about 10.
  • the ratio of Dso particle size (in pm) of the micro silicon active material particles and the BET surface area (m 2 /g) of the micro silicon active material particles may be at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments or examples, the ratio of Dso particle size (in pm) of the micro silicon active material particles and the BET surface area (m 2 /g) of the micro silicon active material particles may be less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1.
  • the ratio of Dso particle size (in pm) of the uncoated micro silicon active material particles and the BET surface area (m 2 /g) of the uncoated micro silicon active material particles may be in a range of between about 0.1 to about 10, about 0.1 to about 9, about 0. 1 to about 8, about 0.1 to about 7, about 0.1 to about 6, about 0.1 to about 5, about 0.5 to about 10, about 0.5 to about 9, about 0.5 to about 8, about 0.5 to about 7, about 0.5 to about 6, about 0.5 to about 5, about 1 to about 10, about 1 to about 9, about 1 to about 8, about 1 to about 7, about 1 to about 6, or about 1 to about 5.
  • a ratio of Dso particle size (in pm) of the micro silicon active material particles and the BET surface area (m 2 /g) of the micro silicon active material particles in the range of about 1.0 to about 3.5 provided by a Dso particle size and BET surface area range of about 3.0 pm to about 6.0 pm and about 1.0 m 2 /g to about 3.5 m 2 /g, respectively, advantageously provided the most improved capacity retention in the full cell configuration for the micro silicon anode design. It will be appreciated that a gradual decrease in electrochemical performance is found when the Dso particle size/BET surface area ratio is higher than 3.5 and lower than 1.0.
  • the low surface reactivity and thus the low irreversible consumption of Li + ions in the micro silicon materials with a high dso particle size (preferably 2.0 - 8.0 pm), low BET surface area (preferably 1.0 - 5.0 m 2 /g) and high dso particle size : BET surface area ratio (preferably 0.1 - 6.0) during cycling extend the capacity retention and cycle life. It was surprisingly found that specific combinations of dso and BET surface area can lead to exceptionally good performance in full cells.
  • the tap density of the micro silicon active material particles or the coated micro silicon active material particles may be in a range of from about 0.5 g/cm 3 to about 1.5 g/cm 3 .
  • the tap density of the micro silicon active material particles or the coated micro silicon active material particles may be at least about 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.2, 1.3 or 1.5 g/cm 3 .
  • the tap density of the micro silicon active material particles or the coated micro silicon active material particles may be less than about 1.5, 1.4, 1.3, 1.2, 1.0, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, or 0.5 g/cm 3 . Combinations of these density values to form various ranges are also possible, for example the micro silicon active material particles or the coated micro silicon active material particles may have a tap density of between about 0.5 g/cm 3 to about 1.2 g/cm 3 . The density can be measured by any standard method, for example in accordance with ASTM D7481-18.
  • the purity of micro silicon active material particles (with oxygen) may be in a range from (by wt.%) about 79 to about 99.5.
  • the purity of micro silicon active material particles (with oxygen) may be at least (by wt.%) about 75, 80, 85, 90, 95, 96, 97, 98, 99 or 99.5.
  • the purity of the micro silicon active material particles (with oxygen) may be less than (by wt.%) about 99.5, 99, 98, 97, 96, 95, 90, 85, 80, or 75.
  • the purity of micro silicon active material particles (with oxygen) may be in a range provided by any lower and/or upper limit as previously described.
  • the combination of novel and inventive features of the micro silicon active material particles according to the present disclosure, their optional coating and their use in an optionally coated anode composition for an anode in a lithium ion battery surprisingly leads to an improvement in the batteries cycle behaviour.
  • the coated micro silicon active material particles according to the present disclosure and their use in an optionally coated anode composition for an anode in a lithium ion battery may also surprisingly lead to an improvement in the batteries cycle behaviour. It was unexpectedly shown that the lithium-ion batteries, as described herein, have a small irreversible capacity loss in the first charge cycle and a stable electrochemical behaviour with minimal fading in the subsequent cycles.
  • the lithium-ion batteries as described herein provide very good stability and cycle life. Accordingly, a high number of cycles can be achieved with minimal fatigue, for example, as a consequence of mechanical destruction of the anode coating layer, anode material or SEI formation.
  • the SEI layer is formed during the intercalation of lithium-ions, where the organic electrolyte is reduced on the anode’s surface when the anode potential is below about IV versus Li+/Li.
  • the SEI layer is crucial in preventing the co-intercalation of electrolyte ions into the bulk electrode material, by creating a fdm that is electrically insulating but ionically conductive. This prevents ongoing excessive decomposition of the electrolyte.
  • some lithium ions may be irreversibly trapped in the electrode, leading to the consumption of lithium ions.
  • the initial irreversible lithium loss of anodes can be compensated by adding lithium to the anode via prelithiation.
  • Prelithiation methods can be broadly grouped into electrochemical prelithiation and chemical prelithiation. Electrochemical prelithiation may be further grouped into half-cell prelithiation or short-circuit prelithiation.
  • Prelithiation at the particle level may be carried out before a coating layer is applied to the particle. It should be noted that the current disclosure is not limited to a particular method of prelithiation and that the most suitable method will be chosen to achieve the intended outcome. [0140] Prelithiation may be applied to anode electrodes. For example, prelithiation may be applied to compensate for the lithium that is lost on first cycle which constitutes one full charge and one full discharge of the electrochemical cell.
  • the amount of prelithiation is chosen such that an SEI layer is formed but no lithium is intercalated or alloyed with the active material before assembly into a full cell, then the first cycle loss of the anode once incorporated into a full cell will be minimized and any further loss of lithium is expected to be contributed from other sources such as the cathode electrode.
  • the electrochemical cell now cycles at a higher cell capacity as more lithium is available in subsequent cycles to be passed back and forth between the anode and the cathode during repeated charge and discharge cycling.
  • Prelithiation may also provide a lithium reservoir in the anode before the anode is assembled into a cell assembly in addition to compensating for any lithium loss that occurs during the first cycle and more generally the initial formation cycles.
  • the lithium reservoir may compensate for ongoing lithium losses over a number of cycles thus reducing capacity fade and extending the useful life of the full cell.
  • prelithiation may provide one or more advantages for silicon containing anodes and in particular for anodes that contain a high percentage of silicon.
  • Providing the anode with a lithium reservoir using a method that also applies an SEI layer to the active material can also maximize the first cycle efficiency of the cell.
  • the anode composition may provide a prelithiated anode composition.
  • the prelithiation may occur at the anode active material level before the active material is incorporated into the anode composition or the prelithiation may occur after the anode composition has been prepared.
  • One or more advantages of the present disclosure are provided by prelithiating the anode composition which can provide a lithium reservoir in the anode thereby extending its cycle life by compensating for ongoing Li + losses during charge/discharge cycling, once incorporated into a full cell arrangement.
  • the micro silicon active material particles or coated micro silicon active material particles may be prelithiated micro silicon active material particles or coated micro silicon active material particles, wherein prelithiation occurs prior to incorporation of the active material into the anode composition. It will be appreciated that the micro silicon active material particles may be prelithiated prior to forming the coated micro silicon active material particles. In other embodiments, the micro silicon active material particles or coated micro silicon active material particles may be prelithiated micro silicon active material particles or coated micro silicon active material particles, wherein prelithiation occurs after the active material has been incorporated into the anode composition.
  • the degree of prelithiation may be chosen such that the created phase is in between LioSii (0% prelithiation) to ITwoSii (100% prelithiation). Any phase composition in between may be desirable including LiiSii, Li i.7iSi2, LiaSii, Lis.sSii, and Lis jsSii.
  • the amount of prelithiation of the micro silicon active material particle and/or the anode composition may be between about 1% and about 30%.
  • the amount of prelithiation of the micro silicon active material particle or coated micro silicon active material particle and/or the anode composition may be less than about 30%, 25%, 20%, 15%, 10%, 5% or 1%.
  • the amount of prelithiation of the micro silicon active material particle or coated micro silicon active material particle and/or the anode composition may be at least about 1%, 5%, 10%, 15%, 20%, 25%, or 30%.
  • the amount of prelithiation of the micro silicon active material particle or coated micro silicon active material particle and/or the anode composition may be in a range provided by any two of these upper and/or lower amounts.
  • Prelithiation of the micro silicon active material particles or coated micro silicon active material particles may be carried out via physical vapor deposition (PVD) or chemical vapor deposition (CVD) or mechanical alloying processes or chemical processes or electrochemical processes. It will be appreciated that a range of suitable methods may be applied to create a silicon-lithium alloy phase prior to the prelithiated micro silicon active material particles being incorporated into the anode composition.
  • the anode composition as described herein may further comprise one or more further active materials.
  • the further active materials may be a graphite or a silicon.
  • flake graphite, natural graphite, artificial graphite, silicon oxide where x 0.8 to 2 (SiOx), silicon carbon composites, silicon alloys, or any combination thereof .
  • the anode composition as disclosed herein may further comprise one or more binders.
  • the binder may be a polymer.
  • the polymer may be selected from the group consisting of gum arabic, carboxymethyl cellulose (CMC)Zcitric acid, CMC/styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), poly(l -trimethylsilyl- 1 -propyne) (PTMSP), gum binders such as gum arabic, Xanthan gum, and guar gum, natural cellulose based binders, polysaccharides such as sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, sodium alginate, polyacrylates, aliphatic polymers such as polyvinyl butyral, aromatic polymers such as styrene-butadiene rubber.
  • the polymer may be selected from the group consisting of polyvinylpyrrolidone, carboxymethylcellulose, polyacrylic acid (PAA), poly(methacrylic acid), maleic anhydride copolymers including polyethylene and maleic anhydride) copolymers, polyvinyl alcohol, carboxymethyl chitosan, natural polysaccharide, Xanthan gum, alginate, polyimide and PAA copolymers including one or several of the following of polyvinylalcohol (PVA), polyurethane (PU), polyimide (PI) or polyacrylonitrile (PAN),
  • the binder is PAA.
  • the binder may be dissolved in H2O or ethanol or mixtures of H2O and ethanol or A A 5 dimethylformamide or any other solvent that is suitable for the intended purpose. Some binders may be present in the form of waterbased emulsions.
  • the ratio of binder to micro silicon active material particles or coated micro silicon active material particles may be about 1:40, 1:35, 1:32, 1 :30, 1:25, 1:23, 1:20, 1: 15, 1: 10, 1:9, 1:6, or 1:4.
  • the ratio ofbinderto micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1:4 to about 1:32.
  • the ratio ofbinder to micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1:8 to about 1:23.
  • the ratio ofbinder to micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1:9 to about 1: 15.
  • the binder (in wt.%) may be present in the anode composition in a range of about 2.5 to 15.
  • the binder (wt.%) may be present in the anode composition in an amount of less than about 15, 12, 10, 8, 5 or 2.5.
  • the binder (in wt.%) may be present in the anode composition in an amount of at least about 2.5 %, 5 %, 8 %, 10 %, 12 %, or 15 %.
  • the binder (in wt.%) may be present in the anode composition in a range provided by any two of these upper and/or lower amounts.
  • the binder (in wt.%) may be present in the anode composition in a range of about 3 to about 8, or about 4 to about 8.
  • the pH of the binder may impact the electrochemical performance of the anode composition.
  • the pH of the binder may be less than 9, 8, 7, 6, 5, 4, 3, or 2.
  • the pH of the binder may be at least 2, 3, 4, 5, 6, 7, 8 or 9.
  • the pH of the binder may be in a range provided by any two of these upper and/or lower values.
  • the pH of the binder may be in a range of 4 to 8.
  • the carbonbased material may be selected from the group consisting of graphene, graphene oxide, graphite, single walled (SWCNT) or multiwalled (MWCNT) carbon nanotubes, branched carbon nanotubes, carbon nanofiber, MXene, nano or micro-sized hard carbons, nano or micro-sized porous carbons and conductive polymer.
  • the ratio of conductive material to micro silicon active material particles or coated micro silicon active material particles may be about 1:50, 1:48, 1:45, 1:40, 1:35, 1:30, 1:25, 1:20, 1: 18. 1: 15, 1: 10, 1:8, 1:6, 1:4, 1:3, 1:2, or 1: 1.3.
  • the ratio of conductive material to micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1:2 to about 1:30.
  • the ratio of conductive material to micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1:2 to about 1: 18.
  • the ratio of conductive material to micro silicon active material particles may be in a range of about 1 : 2 to about 1: 15.
  • the conductive material may be present in the anode composition in a range of about 2.5 to 40 wt.% (based on total weight of the anode composition).
  • the conductive material may be present in the anode composition in an amount (based on total weight of the anode composition) of less than about 40 wt.%, 30 wt.%, 20 wt.% 15 wt.%, 10 wt.%, 7 wt.%, 5 wt.% or 2.5 wt.%.
  • the conductive material may be present in the anode composition in an amount (based on total weight of the anode composition) of at least about 2.5 wt.%, 5 wt.%, 7 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 30 wt.%, or 40 wt.%.
  • the conductive material may be present in the anode composition in an amount provided by any two of these upper and/or lower amounts.
  • the conductive material may be present in the anode composition in an amount between about 7 wt.% and about 25 wt.%.
  • the present disclosure is directed to providing improvements in anodes for an electrochemical cell.
  • the present disclosure is directed to an anode for an electrochemical cell comprising an anode composition at least according to some embodiments or examples as described herein.
  • capacity limitation may be considered in terms of mass loading or area capacity.
  • Mass loading or area capacity refers to an electrochemical cell assembly where the capacity of the anode may be significantly oversized relative to the cathode.
  • the capacity limitation may have the effect of limiting the capacity of the oversized electrode (anode) by only allowing for a partial lithiation to occur as the amount of lithium that is contained in the electrochemical cell is limited by the lithium contained in the cathode upon cell assembly.
  • the resulting estimated percentage capacity limitation is calculated by y/x * 100. It will be appreciated that this approach to capacity limitation may be particularly useful in situations where the anode contains a high percentage of elemental silicon as the active material which offers specific capacities in excess of 3500 mAh/g.
  • the specific area capacity (in mAh/cm 2 ) corresponding to the full utilization of the active materials contained within the anode composition of the anode may be in between 2.5 mAh/cm 2 to 20 mAh/cm 2 .
  • the specific loading weight (in mg/cm 2 ) of the anode composition may be in between 0.95 mg/cm 2 to 7.5 mg/cm 2 .
  • capacity limitation may be considered in terms of the phase composition of the LiSi alloy.
  • LisjsSi i or lAwSii corresponds to the maximum accessible capacity of 3590 mAh/g or the highest theoretical state of lithitation of 4200 mAh/g. It will be understood that if utilization of the anode is limited this may translate into specific phase compositions of the LiSi alloy. Specific phase compositions may also translate into a specific capacity (mAh/g).
  • Lii.7iSii may correspond to a specific capacity of up to 1636 mAh/g
  • Li2.33 Si may correspond to a specific capacity of up to 2227 mAh/g
  • Lis 2sSi i may correspond to a specific capacity of up to 3101 mAh/g
  • Lis jsSii may correspond to a specific capacity of up to 3579 mAh/g
  • Li4.4Sii may correspond to a specific capacity of up to 4199 mAh/g.
  • capacity limitation may be considered in terms of the voltage of the anode during charge and/or discharge. It will be understood that amount of silicon lithiation after discharge may be configured by a discharge voltage of the anode.
  • the N/P ratio balance between anode and cathode may be in between about 1.05 and about 7, and/or the voltage range may be controlled with respect to level of discharge of the electrochemical cell.
  • the capacity of the lithium uptake capacity of the anode may not be fully utilized during charging of the lithium ion battery.
  • the specific area capacity of the anode may be greater than the specific area capacity of the cathode. In other words, the anode is only partially lithiated in the fully charged state.
  • the Li/Si ratio of an electrochemical cell may be set by the anode to cathode ratio (N/P).
  • the N/P ratio between anode and cathode may be in between about 1.05 and about 7, about 2 and about 5, or about 3 and about 4.
  • the N/P ratio may be than about 7, 6, 5, 4, 3, 2, or 1.05.
  • the N/P ratio may be at least about 1.05, 2, 3, 4, 5, 6, or 7.
  • the N/P ratio may be in a range provided by any two of these upper and/or lower values.
  • the N/P ratio between anode and cathode may be in between about 1.5 and about 4, or between about 1.8 and about 3.5.
  • the capacity limitation (in %) may be at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 0, 85, 90, 95, or 99. In some embodiments, the capacity limitation (in %) may be less than about 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20.
  • the capacity limitation (in %) may be in a range provided by any two of these upper and/or lower values. For example, the capacity limitation (in %) may be in between about 25 and about 90, or between about 30 and about 80.
  • the present disclosure advantageously provides an electrochemical cell that is designed so that the lithium uptake capacity of the anode is greater than the lithium release capacity of the cathode.
  • a high N/P ratio may limit the degree of lithiation of the micro silicon, as the amount of Li ion is fixed by the cathode upon cell assembly.
  • the anode may be significantly oversized relative to the amount of lithium that is contained in the cell and provided by the cathode.
  • the degree of lithiation is limited by the oversized anode so is the level of expansion of the micro silicon active material particles or coated micro silicon active material particles and its degradation.
  • the degree of silicon lithiation may be in a range of about 20% to about 80%. Unexpectedly, the degree of silicon lithium in this range may have a stabilizing effect on the electrochemical cells performance.
  • the capacity of the electrochemical cell can be limited by limiting the lower cut-off voltage.
  • the lower cutoff voltage may be between about 2.5V and about 3.0V.
  • the lower cut-off voltage may be between 2.8V and about 3.0V. It will be appreciated that a voltage limitation may be applied by restricting the lower cut-off voltage. This can prevent the complete delithiation of the micro silicon active material particles or coated micro silicon active material particles at each cycle and mitigate its expansion, leading to less degradation and consequently extended cycle life.
  • the capacity of the electrochemical cell can be limited by limiting the upper cut-off voltage.
  • the upper cutoff voltage may be between about 3.6V and about 4.25V.
  • the anode composition may be prelithiated as described in any one of more of the embodiments or examples described hereon. In some embodiments, prelithiation may occur prior to incorporation of the active material into the anode composition. In other embodiments, prelithiation may occur after the active material has been incorporated into the anode composition. In some embodiments or examples, the amount of prelithiation of the anode composition may be between about 1% and about 30%. The amount of prelithiation of the anode composition may be less than about 30%, 25%, 20%, 15%, 10%, 5% or 1%. The amount of prelithiation of the anode composition may be at least about 1%, 5%, 10%, 15%, 20%, 25%, or 30%. The amount of prelithiation of the anode composition may be in a range provided by any two of these upper and/or lower amounts.
  • the amount of lithium contained in the anode may be about 30% of its maximum storage capacity while the cathode may contain 100% of its maximum storage capacity. In some embodiments, the amount of lithium contained in the anode may be about 20% of its maximum storage capacity while the cathode may contain 100% of its maximum storage capacity. In some embodiments, the amount of lithium contained in the anode may be about 10% of its maximum storage capacity while the cathode may contain 100% of its maximum storage capacity.
  • a first cycle loss can be estimated upon having tested the corresponding composition in a half cell against a lithium metal foil reference electrode and having so determined the anode compositions first cycle loss. If the first cycle loss is estimated to be x%, then to create a lithium reservoir of y%, the initial lithiation step during the prelithiation process needed to achieve a lithiation level of the silicon anode composition of z% needs to account for x% + y%.
  • an anode composition shows a first cycle loss of 10%
  • this loss needs to be taken into account when calculating the desired degree of prelithiation to obtain the resulting lithium reservoir.
  • the anode may be lithiated up to 20% of its expected design capacity (mAh/g) where the initial -10% aim to compensate for the irreversible lithium loss during the first cycle and the additional are stored in the anode or the silicon material and thus form the desired lithium reservoir.
  • the maximum desired level of a lithium reservoir may be 30%.
  • pairing prelithiation and capacity limitation may provide the electrochemical cell of the present disclosure with one or more further advantages.
  • the capacity of the anode that is occupied by lithium that is supplied by the cathode and stored in the anode on first lithiation will be the same with and without prelithiation notwithstanding any loss of lithium on first cycle, the lithium reservoir in the anode can compensate for the gradual loss of lithium during repeated charge and discharge cycling for a number of cycles.
  • the anode composition may be applied to a current collector material as a coating or film.
  • the current collector material for the anode may be selected from the group comprising copper, aluminium, stainless steel, titanium, carbon, perforated metal foils, metal foams, and metal coated polymer based porous and non-porous membranes.
  • the anode composition may be applied to a copper current collector material (e.g. copper foil).
  • the current collector material for the anode may have a thickness of between about 4 pm and about 25 pm.
  • the thickness of the current collector (in pm) may be less than about 25, 20, 15, 10, 8, 6, or 4.
  • the thickness of the current collector (in pm) may be at least about 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, or 25.
  • the thickness of the current collector (in pm) may be in a range provided by any two of these upper and/or lower amounts.
  • the current collector material for the anode may be copper foil having a thickness of between about 6 pm and about 12 pm.
  • the cathode active material is also applied to a current collector material.
  • the current collector material for the anode may be selected from the group comprising copper, aluminium, stainless steel, titanium, carbon, perforated metal foils, metal foams, and metal coated polymer based porous and non- porous membranes.
  • the cathode composition may be applied to an aluminium current collector material (e.g. aluminium foil).
  • the current collector material for the cathode may have a thickness of between about 10 pm and about 30 pm.
  • the thickness of the current collector (in pm) may be less than about 30, 25, 20, 15, or 10.
  • the thickness of the current collector (in pm) may be at least about 10, 12, 14, 16, 18, 20, 25, or 30.
  • the thickness of the current collector (in pm) may be in a range provided by any two of these upper and/or lower amounts.
  • the current collector material for the cathode may be aluminium foil having a thickness of between about 10 pm and about 30 pm.
  • the cathode may be selected from the group consisting of lithium nickel cobalt manganese oxide (NCM), lithium iron phosphate (LFP), lithium nickel manganese spinel (LNMO), lithium nickel cobalt aluminium oxide (NCA), lithium manganese oxide (LMO), lithium cobalt oxide (LCO), and sulphur or sulphur composite including sulphur and carbon mixtures.
  • NCM lithium nickel cobalt manganese oxide
  • LFP lithium iron phosphate
  • LNMO lithium nickel manganese spinel
  • NCA lithium nickel cobalt aluminium oxide
  • LMO lithium manganese oxide
  • LCO lithium cobalt oxide
  • sulphur or sulphur composite including sulphur and carbon mixtures.
  • the electrolytes may be selected from a non-aqueous solution of one or more lithium salts (e.g. in Li-ion cells).
  • the one or more lithium salts may be selected from the group comprising lithium bis(trifluoromethane sulfone)imide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis(trifluorosulfonylimide), lithium trifluoromethanesulfonate, lithium fluoroalkylsulfonimides, lithium fluoroarylsulfonimides, lithium bis(oxalate borate), lithium tris(trifhioromethylsulfonylimide)methide, lithium difluoromethane sulfonate, trifluoromethanesulfonic acid lithium salt (lithium triflate), lithium bis(oxalato)borate, lithium tetrafluoroborate, lithium perchlorate, lithium t
  • the lithium salt may be dissolved in an organic solvent.
  • the lithium salt may be dissolved in an organic solvent selected from ethers, esters, carbonates, and acetals.
  • the solvent may be selected from dimethoxyethane, diglyme, triglyme, tetraglyme, ethylene carbonate, propylene carbonate, dimethyl carbonate, tetrahydrofuran, and dioxolane.
  • the lithium salt may be dissolved in an organic solvent selected from the group comprising ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, butylmethyl carbonate, ethylpropyl carbonate, dipropyl carbonate, cyclopentanone, sulfolane, dimethyl sulfoxide, 3-methyl-l,3-oxazolidine-2-one, y-butyrolactone, 1,2- diethoxymethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,2- dimethoxyethane, methyl acetate, ethyl acetate, nitromethane, 1,3-propane sultone, y- valerolactone, methyl isobutyryl acetate, 2-methoxyethyl acetate, 2-
  • the electrolyte may comprise an additive selected from one or more alkali metal salts of LiPFe LiBF4, LiAsFe, LiSbFe, LiCICh, LiAlCb, LiGaCh. LiC(SC>2CF3)3, LiN(SO 2 CF 3 )2, LiSCN, LiSO2CF 2 CF3, LiCeFsSCh, LiO 2 CCF3, LiSCEF, LiB(C 6 H 5 )4, LiCF3SC>3, LiNOi. and mixtures thereof.
  • LiPFe LiBF4 LiAsFe, LiSbFe, LiCICh, LiAlCb, LiGaCh. LiC(SC>2CF3)3, LiN(SO 2 CF 3 )2, LiSCN, LiSO2CF 2 CF3, LiCeFsSCh, LiO 2 CCF3, LiSCEF, LiB(C 6 H 5 )4, LiCF3SC>3, LiNOi. and mixtures thereof.
  • the additive may be selected from one or more of flouroethylene carbonate (FEC), vinylethylene carbonate (VEC), vinyl carbonate (VC), propylene carbonate (PC), ethylmethyl carbonate (EMC), propane sultone (PS), and mixtures thereof.
  • Electrolyte additives can further improve certain characteristics of the cell.
  • the electrolyte e.g. lithium hexafluorophosphate
  • the lithium salt may be dissolved in one or more organic solvents as described above, wherein the one or more organic solvents are present in a volume to volume ratio ranging from 10 to 1 to 1 to 10.
  • the lithium salt e.g., IM LiPFe
  • a separator is used to electrically separate the anode from the cathode, and allowing free passage of lithium ions in the electrolyte.
  • the separator may be selected from a range of different porous polymer films. It will be appreciated that any porous polymer film may be selected for use as a separator that have a suitable porosity, tortuosity and thickness.
  • a polymer film-based separator material may be selected.
  • the separator may be selected from a polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET).
  • a non-woven fibrous material be selected as the separator, comprising of fibres selected from nylon, polyethylene terephthalate (PET), cellulose, aramid or polyacrylonitrile.
  • the electrochemical cell may be an energy storage device.
  • the energy storage device may be a battery.
  • the battery may be a secondary battery.
  • the battery may be a lithium ion battery (Li-ion battery).
  • the specific capacity (mAh/g) may be at least about 500, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800,3000 or 3500. In some embodiments or examples, the specific capacity (mAh/g) may be less than about 3500, 3400, 3200, 3000, 2800, 2600, 2400, 2200, 2000, 1800, 1600, 1400, 1200, 1000, 800, 600 or 500. The specific capacity (mAh/g) may be in a range provided by any two of these upper and/or lower values.
  • the number of cycles may be at least 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 1000 or 1500.
  • the long term cyclic performance of an electrochemical cell (e.g. Li-ion battery) comprising the anode composition may be tested for high silicon content anodes (i.e. about 70 % silicon content) with varying capacity limitation.
  • the initial discharge capacity of the anode comprising the anode composition can be at least about (in mAh/g) 600, 800, 1100, 1200, 1300, 1400, 1500, or 1600. At least according to some embodiments or examples, 80% of the discharge capacity may be retained after cycles of 100, 200, 300, 400, 500, 800, 1000 or 1500.
  • galvanostatic charge-discharge cycling experiments may typically be used to evaluate the performance metrics of a battery: capacity, rate capability, coulombic efficiency, and capacity retention upon cycling.
  • the present disclosure is also directed to an anode comprising an anode composition, wherein the anode may be a battery anode. More particularly, a lithium ion battery anode.
  • the optionally coated anode composition which may comprise or consist of optionally coated micro silicon active material particles, optionally one or more binders, optionally one or more conductive materials, and optionally one or more additives, significantly reduces effects shown by SEI formation and silicon expansion and degradation, and therefore provides improved performance of Li-ion batteries.
  • the anode composition provides a high first cycle efficiency, and further advantages providing controlled silicon utilization, which, in turn, improves the high current response and performance of the battery.
  • an electrochemical cell e.g., Li-ion battery
  • an electrochemical cell comprising the anode composition as described herein, allows partially utilization/lithiation of silicon and the specific capacity of the anode is reduced and controlled by the amount of lithium the cathode is able to supply, providing an improved average Coulombic efficiency (CE) of at least about 75, 80, 85, 90, 95, 98%, 99%, 99.5%, 99.8% , 99.9% or higher or less than 100% over at least 200 cycles.
  • CE Coulombic efficiency
  • use of the anode composition as an anode provides improved performance of Li-ion batteries showing cyclic stability after at least 200 cycles at C/2.
  • the N/P ratio for an anode that contains majority micro-silicon (e.g., >70%) is manipulated to a value of above 3 (e.g., 3.3), stable cycling of the anode can be provided to achieve more than 200 cycles at greater than 80% capacity retention.
  • the high N/P ratio limits the degree of lithiation of the micro-silicon, as the amount of Li + is fixed by the cathode upon cell assembly. This leads to a degree of silicon lithiation of about 20% to about 80%, instead of 80% to 90% as seen for the conventional cell assembly where the anode comprises majority graphite, which has a stabilizing effect on the cells performance.
  • the anode is significantly oversized relative to the amount lithium that is contained in the cell and provided by the cathode.
  • the degree of lithiation is limited by the oversized anode so is the level of expansion of the silicon and its degradation.
  • the present disclosure is directed to a process for preparing an anode for an electrochemical cell.
  • the process will include at least one of incorporating coated micro silicon active material particles into the anode or coating the anode itself either during or following its formation.
  • the process may be for preparing an anode according to any embodiments or examples as described herein. It will be appreciated that the anode prepared by the process may comprise an anode composition comprising micro silicon active material particles or coated micro silicon active material particles.
  • micro silicon active material particles, coated micro silicon active material particles, one or more further active materials, one or more optional binder, one or more optional conductive materials, one or more optional additives, and one or more optional solvents may be selected from any one or more of the embodiments or examples as described herein.
  • a process for preparing a coated micro silicon active material particle comprising: (i) providing a plurality of micro silicon active material particles, wherein the micro silicon active material particles have (i) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g and (ii) a Dso particle size between about 0. 1 pm and about 10 pm, or (iii) a ratio of D50 : BET surface area between about 0.1 to about 10; and (ii) applying a coating onto the surface of the micro silicon active material particles.
  • a process for preparing of an anode for an electrochemical cell comprising the steps of: (i) preparing an anode slurry comprising micro silicon active material particles or coated micro silicon active material particles, optionally one or more further active materials, optionally one or more binders, optionally one or more conductive materials, optionally one or more additives, and a solvent system; (ii) casting a layer of the anode slurry onto a current collector material to provide a anode composition layer on the current collector material; and (iii) optionally coating the anode composition, wherein the micro silicon active material particles have one or more of the following: (a) a measured BET surface area between about 0. 1 m 2 /g and about 10 m 2 /g, (b) a D50 particle size between about 0. 1 pm and about 10 pm, and (c) a ratio of D50 : BET surface area between about 0. 1 to about 10.
  • a process for preparing of an anode for an electrochemical cell comprising the steps of: (i) preparing an anode slurry comprising micro silicon active material particles or coated micro silicon active material particles, optionally one or more further active materials, optionally one or more binders, optionally one or more conductive materials, optionally one or more additives, and a solvent system; (ii) casting a layer of the anode slurry onto a current collector material to provide a anode composition layer on the current collector material; and (iii) optionally coating the anode composition, wherein the micro silicon active material particles have (a) a measured BET surface area between about 0.1 m 2 /g and about 10 m 2 /g and (b) a D50 particle size between about 0. 1 pm and about 10 pm or (c) a ratio of D50 : BET surface area between about 0.1 to about 10.
  • the process may further comprise step (iii) solidifying the wet anode layer by solvent evaporation to provide a dry anode composition layer on the current collector material.
  • the coating may be selected from the group comprising carbon, graphene, graphite, metal oxide, polymer, and combinations thereof, to form a coated micro silicon active material particle or a coated anode composition.
  • the coating may be selected from the group comprising carbon, graphene, graphite, metal oxide, polymer, and combinations thereof, to form a coated micro silicon active material particle or a coated anode composition.
  • the coatings may be from the materials and made by the approaches as described in any of the aforementioned embodiments relating to the coatings of the disclosure and/or the silicon particles of the disclosure with the coatings so applied.
  • the solvent may be an organic solvent selected from aromatics, halogenated aromatics, halogenated aliphatic hydrocarbons, aliphatic hydrocarbons, glycols, ethers, glycol ethers, esters, alcohols, ketones, or combinations thereof.
  • the solvent may be present in an amount (by weight % of total anode composition) between about 40 wt.% and 90 wt.%, between about 40 wt.% and 70 wt.%, or between about 40 wt.% and 60 wt.%.
  • the solvent may be a low boiling point organic solvent, or a mixture of one or more of such solvents.
  • the solvent may be selected from the group comprising water, methanol, ethanol, n-propanol, isopropanol, tetrahydrofuran, methylene chloride, chloroform, diethyl ether, room temperature ionic liquids, ethylene glycol, glycerol, formamide, JV-methylformamide, dimethylformamide, N- methylsydnone, an aqueous solution thereof, and any mixtures thereof.
  • the solvent may be water, ethanol, N.N' dimethylformamide, or a combination thereof.
  • the ratio of binder to micro silicon active material particles may be about 1:40, 1:35, 1:32, 1:30, 1:25, 1:23, 1:20, 1: 15, 1: 10, 1:9, 1:6, or 1:4.
  • the ratio of binder to micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1:4 to about 1:32.
  • the ratio of binder to micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1:8 to about 1:23.
  • the ratio of binder to micro silicon active material particles or coated micro silicon active material particles may be in a range of about 1 : 9 to about 1: 15.
  • the binder (in wt.%) may be present in the anode composition in a range of about 2.5 to 15 .
  • the binder (wt.%) may be present in the anode composition in an amount of less than about 15, 12, 10, 8, 5 or 2.5.
  • the binder (in wt.%) may be present in the anode composition in an amount of at least about 2.5 %, 5 %, 8 %, 10 %, 12 %, or 15 %.
  • the binder (in wt.%) may be present in the anode composition in a range provided by any two of these upper and/or lower amounts.
  • the binder (in wt.%) may be present in the anode composition in a range of about 3 to about 8, or about 4 to about 8.
  • the viscosity of the anode slurry may be in a range between about 10 mPas and 100,000 mPas.
  • the viscosity (mPas) may be less than about 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 8000, 6000, 4000, 2000, 1000, 800, 600, 400, 200, 100, 50, or 10 at a given shear rate.
  • the viscosity may be at least about 10, 20, 40, 60, 80, 100, 300, 500, 700, 900, 1000, 3000, 5000, 7000, 9000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000 at a given shear rate.
  • the viscosity (mPas) of the anode slurry may be in a range provided by any two of these upper and/or lower amounts.
  • viscosity (mPas) of the anode slurry may be in a range of about 2500 mPas to about 8000 mPas at a given shear rate. All viscosity values recited herein may be at a given shear rate.
  • the shear rate may be that as used in any accepted standard testing approach in the art.
  • the thickness of the dry anode composition may be substantially uniform and in the range of about 5 pm to about 70 pm.
  • the thickness (pm) of the dry anode composition may be less than about 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5.
  • the thickness (pm) of the dry anode composition may be at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65.
  • the thickness of the dry anode composition may be in a range provided by any two of these upper and/or lower amounts.
  • the wet anode composition layer may be maintained at a temperature of between about 40 °C and about 60 °C in step (iii)(a) for about 30 seconds to about 5 minutes.
  • the wet anode composition may be maintained at a temperature (°C) of less than about 60, 55, 50, 45, or 40.
  • the wet anode composition may be maintained at a temperature (°C) of at least about 40, 45, 50, 55, or 60.
  • the wet anode composition may be maintained at a temperature (°C) in a range provided by any two of these upper and/or lower values.
  • the wet anode composition may be maintained at a temperature as described herein for less than about 24 hours, 12 hours, 8 hours, 4 hours, 2 hours, 1 hours, 30 minutes, 5 minutes, 4 minutes, 3 minutes, 2 minutes, 1 minute, or 30 seconds.
  • the wet anode composition may be maintained at a temperature as described herein for at least about 30 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 10 hours, 12 hours, or 24 hours.
  • the wet anode composition may be maintained at a temperature as described herein for a time in a range provided by any two of these upper and/or lower values.
  • the wet anode composition may be maintained at a temperature of between about 90 °C and about 180 °C in step (iii)(b) for about 30 seconds to about 5 minutes.
  • the wet anode composition may be maintained at a temperature (°C) of less than about 180, 170, 160, 150, 140, 130, 120, 115, 110, 105, 100, 95 or 90.
  • the wet anode composition may be maintained at a temperature (°C) of at least about 90, 95, 100, 105, 110, 115, 120, 130, 140, 150, 160, or 170.
  • the wet anode composition may be maintained at a temperature (°C) in a range provided by any two of these upper and/or lower values.
  • the wet anode composition may be maintained at a temperature as described herein for less than about 24 hours, 12 hours, 8 hours, 4 hours, 2 hours, 1 hours, 30 minutes, 5 minutes, 4 minutes, 3 minutes, 2 minutes, 1 minute, or 30 seconds.
  • the wet anode composition may be maintained at a temperature as described herein for at least about 30 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 10 hours, 12 hours, or 24 hours.
  • the wet anode composition may be maintained at a temperature as described herein for a time in a range provided by any two of these upper and/or lower values. 10212 ]
  • the anode slurry can be made homogeneous to provide further advantage s/improvements.
  • the present disclosure is directed to a process for assembling an electrochemical cell, whereby the process may comprise the steps of: preparing an anode as defined by the process at least according to any one of the examples described herein, wherein the anode may comprise an anode composition comprising micro silicon active material particles; and assembling the anode into an electrochemical cell.
  • the present disclosure is directed to a process for assembling an electrochemical cell, whereby the process may comprise the steps of: preparing an anode as defined by the process at least according to any one of the examples described herein, wherein the anode may comprise or consist of an anode composition comprising micro silicon active material particles or coated micro silicon active material particles, optionally one or more further active materials, optionally one or more binders, and optionally one or more conductive materials, at least according to any one of the examples described herein; and assembling the anode into an electrochemical cell.
  • anode slurry Upon formation of the anode slurry, some or all of the solvent may be removed (e.g., by natural evaporation, forced evaporation, or under vacuum) to generate a solid or viscous anode slurry.
  • the anode slurry may be formed or moulded in any desired shape, such as an anode.
  • the anode slurry may also be deposited on a current collector material, as defined herein, to generate an anode.
  • a current collector material as defined herein.
  • the anode is the combination of the current collector material and the anode composition, also referred to as an anode composition applied to a current collector material.
  • the current collector material can be selected from any current collector material referred to herein.
  • the anode composition may be applied to only a portion of the surface of the current collector material.
  • the portion (%) may be less than about 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5.
  • the anode composition may be applied by casting on the current collector material (e.g. roll-to-roll processing).
  • the coating can be prepared by dissolving or dispersing the coating in an appropriate solvent and then mixing them together, optionally with one or more agents or dissolving the coating into a suitable solvent under suitable processing conditions.
  • the coating may be applied in different physical forms such as a solution, dispersion, suspension, mixture, aerosol, emulsion, paste or combination thereof.
  • a process for preparing a coated anode comprises: a. applying a coating as described herein to an anode composition; and b. optionally applying one or more post coating layers to the coating present on the anode composition.
  • the coated anode composition may be provided from pyrolization of a coating or by chemical vapour deposition, physical vapour deposition, sputtering, or mechanical deposition.
  • the coating may be in the form of a single layer. In another embodiment, the coating may be in the form of two or more layers, for example, a plurality of layers.
  • the coating may comprise between about 1 to 5 layers.
  • the coating may comprise less than 5 layers, 4 layers, 3 layers, or less than 2 layers.
  • the coating may comprise at least about 1 layer, 2 layers, 3 layers, 4 layers, or at least about 5 layers.
  • the coating may comprise layers in a range provided by any lower and/or upper limit as previously described. It will be appreciated that each layer may be provided by a different coating.
  • the coated micro silicon active material particles or coated anode composition may comprise a coating, wherein one coating layer comprises a carbon material another coating layer comprises a metal oxide (e.g., aluminium oxide) and another layer comprises a polymeric coating, applied in any order to the micro silicon.
  • the coating may be a carbon material coating and a metal oxide coating, applied in either order to the micro silicon.
  • the coating may be a carbon material coating and a polymeric coating, applied in either order to the micro silicon.
  • the thickness of the coating may be between about 0.1 nm and about 200 nm, or between about 0.2 nm and about 150 nm, or between about 0.3 nm and about 100 nm, or between about 0.3 nm and about 75 nm, or between about 0.3 nm and about 50 nm, or between about 0.3 nm and about 25 nm, or between about 0.3 nm and about 20 nm, or between about 0.3 nm and about 10 nm.
  • the thickness of the coating (in nm) may be less than about 200, 175, 150, 125, 100, 90, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 8, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0. 1.
  • the thickness of the coating (in nm) may be at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80.
  • the thickness of the coating (in nm) may be in a range provided by any two of these upper and/or lower amounts.
  • the ratio of the coating thickness to uncoated silicon particle diameter may be between about 0.0001: 1 to about 0.2: 1, or between about 0.0001: 1 to about 0.15: 1, or between about 0.0001: 1 to about 0.12: 1, or between about 0.0001: 1 to about 0.1: 1, or between about 0.0001: 1 to about 0.09: 1, or between about 0.0001: 1 to about 0.085: 1.
  • the ratio of the silicon particle diameter to coating thickness may be between about 1: 100,000 to about 1:5, or between about 1: 100,000 to about 1:8, or between about 1: 100,000 to about 1: 10, or between about 1: 100,000 to about 1: 12.
  • the coatings on the micro silicon active material particles or the anode composition can improve cycling stability and reduce electrolyte decomposition due to electrochemical protection of the anode surface. It will be appreciated that the coating may provide the micro silicon active particles or anode composition with a number of properties including, for example, structural strength, lower surface area, reduced pulverization, electron conductivity, Li-ion conductivity, passivation and/or insulation, and ultimately improve silicon anode capacity retention.
  • Example 1 General procedure for preparing anodes
  • anode slurry To prepare the anode slurry, a binder solution and a conductive material are combined using a planetary-centrifugal mixer. The mixture is then incorporated at 2000 rpm for 2 minutes, manually mixed with a spatula, and then mixed for another 2 minutes. The micro silicon active material particles and required amounts of additional water are added and the mixing steps are repeated. An active graphite is added, and the mixing steps are repeated. Unless otherwise mentioned a pre-determined amount of anode slurry is transferred to a Dispermat-compatible container and is mixed at 6000 rpm using an overhead mixer (e.g.: VMA-Getzmann Dispermat) for 5 minutes.
  • an overhead mixer e.g.: VMA-Getzmann Dispermat
  • the thickness of the coating that is applied to a micro-silicon particle can be estimated if the surface area of the particle before coating, the weight the coating contributes to the micro-silicon particle powder and the density of the respective coating material are known.
  • the following generic formula is used to estimate the coating thickness of the coatings that were applied to the micro-silicon particles disclosed in any of the following examples, and in all discussion of coating thickness within the present disclosure, where the true density of the coating material is used as an approximation for the resulting coating density:
  • the true coating thickness on the micro-silicon particle may be slightly higher or lower, subject to the properties and actual density of the coating, which will change depending on the coating material and the method of application.
  • the D50 particle size and BET surface area values for the uncoated and AI2O3 coated micro-silicon are as follows.
  • the sample was heated to 900 °C at a heating rate of 4 °C/min and calcined for 1 hour. The furnace was then allowed to cool down to room temperature while maintaining the nitrogen gas flow at least until the furnace temperature reached 100 °C.
  • the calcined micro-silicon sample was ground using a mortar and pestle for approximately 5 minutes to break down any larger chunks of silicon.
  • the product was then ball-milled at 6 minutes milling and 3 minutes resting intervals for total of 3 hours at 520 rpm using a milling ratio of 30 wt% silicon and 70 wt% grinding media (i.e., 1 cm diameter ceramic balls).
  • Example 3.2 7.93 wt% carbon coated micro-silicon
  • Example 3.1 The coating procedure in Example 3.1 was repeated using 40 g of phenolic resin and 104 g of micro-silicon. 65 g of resin-coated micro-silicon was transferred to a ceramic crucible and placed in the furnace tube. The furnace was purged with high purity nitrogen gas at a flow rate of 2 L/min for 30 minutes at room temperature prior to starting the calcination process and maintained throughout. The sample was heated to 900 °C at a heating rate of 4 °C/min and calcined for 2 hours. The furnace was then allowed to cool down to room temperature while maintaining the nitrogen gas flow at least until the furnace temperature reached 100 °C.
  • the calcined micro-silicon sample was ground using a mortar and pestle for approximately 5 minutes to break down any larger chunks of silicon.
  • the product was then ball-milled at 6 minutes milling and 3 minutes resting intervals for total of 3 hours at 520 rpm using a milling ratio of 30 wt% silicon and 70 wt% grinding media (i.e.,1 cm diameter ceramic balls).
  • Table 8 shows that increasing the content of phenolic resin (PR) in the coating effected the ICE.
  • the ⁇ 8wt% PR coating showed a 3.7% decrease in the ICE and a decrease of 2.4% for the ⁇ 6.6 wt.% PR coating when compared to control.
  • the capacity retention for the uncoated was 99.4% whereas for the ⁇ 8wt% PR coated cells capacity retention was 96.2% and for ⁇ 6.6 wt.% PR was 97% ( Figure 2b).
  • the product was then ball-milled at 6 minutes milling and 3 minutes resting intervals for total of 3 hours at 520 rpm using a milling ratio of 30 wt% silicon and 70 wt% grinding media (i.e., 0.7 cm diameter ceramic balls).
  • 37.0 g of PVP-coated micro-silicon was transferred to a ceramic crucible and placed in the furnace tube.
  • the furnace was purged with high purity nitrogen gas at a flow rate of 2 L/min for 30 minutes at room temperature prior to starting the calcination process and maintained throughout.
  • the sample was heated to 700 °C at a heating rate of 4 °C/min and calcined for 1 hour.
  • the furnace was then allowed to cool down to room temperature while maintaining the nitrogen gas flow at least until the furnace temperature reached 100 °C.
  • the coated micro-silicon sample was first ground using a mortar and pestle to break down larger chunks of silicon followed by a laboratory sample mill for 30 minutes.
  • the product was then ball-milled at 6 minutes milling and 3 minutes resting intervals for total of 3 hours at 520 rpm using a milling ratio of 30 wt% silicon and 70 wt% grinding media (i.e., 0.7 cm diameter ceramic balls).
  • Table 11 showed that increasing the content of PVP coating adversely affects the ICE: 3.12 wt% PVP sample showed a slight decrease in ICE of 0.6% when compared to control, whereas the 6.92 wt% PVP sample had lost ⁇ 3% of ICE. At cycle 100, the uncoated sample lost ⁇ 3% of its capacity whereas the 3.1 wt% PVP has lost 5% at the same cycle.
  • Example 5 PAN precursor carbon coated micro-silicon
  • 60 g of the resultant dried product was placed in the furnace tube and the furnace was purged with high purity nitrogen gas at a flow rate of 2 L/min for 30 minutes at room temperature prior to starting the calcination process.
  • the sample was heated to 900 °C at a heating rate of 4 °C/min and calcined for 2 hours.
  • the furnace was then allowed to cool down to room temperature while maintaining the nitrogen gas flow at least until the furnace temperature reached 100 °C.
  • the calcined micro-silicon sample was ground using a mortar and pestle for approximately 5 minutes to break down any larger chunks of silicon.
  • the product was then ball-milled at 6 minutes milling and 3 minutes resting intervals for total of 3 hours at 520 rpm using a milling ratio of 30 wt% silicon and 70 wt% grinding media (i.e., 0.7 cm diameter ceramic balls).
  • the Dso particle size and BET surface area values for the carbon coated micro- silicon are as follows.
  • the C rates were based on the mass of active material (Si particles, graphite) in the electrodes.
  • First lithiation is limited by capacity (mAh/g) to a 20% of the anode expected capacity accounting for a -10% lithium loss on first cycle.

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